Phase change inks containing curable amide gellant compounds

ABSTRACT

Disclosed is a phase change ink comprising a colorant, an initiator, and a phase change ink carrier, said carrier comprising at least one radically curable monomer compound and a compound of the formula  
                 
 
wherein R 1  and R 1 ′ each, independently of the other, is an alkyl group having at least one ethylenic unsaturation, an arylalkyl group having at least one ethylenic unsaturation, or an alkylaryl group having at least one ethylenic unsaturation, R 2 , R 2 ′, and R 3  each, independently of the others, are alkylene groups, arylene groups, arylalkylene groups, or alkylarylene groups, and n is an integer representing the number of repeat amide units and is at least 1. Also disclosed herein is a method of printing with the phase change ink.

CROSS-REFERENCE TO RELATED APPLICATIONS

Copending Application U.S. Ser. No. 11/018,378, filed Dec. 22, 2004,entitled “Curable Phase Change Ink Composition,” with the namedinventors Peter G. Odell, Marcel P. Breton, Christine E. Bedford, andChris A. Wagner, the disclosure of which is totally incorporated hereinby reference, discloses ink compositions that comprise one or moreradiation curable oil soluble components and one or more thermalsolvents, as well as methods of preparing such ink compositions andmethods of using such ink compositions.

Copending Application U.S. Ser. No. 11/004,761, filed Dec. 4, 2004,entitled “Curable Trans-1,2-Cyclohexane Bis[urea-urethane] Compounds,”with the named inventors Rina Carlini, Eniko Toma, Peter G. Odell, andJeffery H. Banning, the disclosure of which is totally incorporatedherein by reference, discloses curable trans-1,2-cyclohexanebis[urea-urethane] compounds of the formulae

wherein R₁ and R₁′ each, independently of the other, are alkylene,arylene, arylalkylene, or alkylarylene groups, R₂ and R₁₂ each,independently of the other, are alkyl, aryl, arylalkyl, or alkylarylgroups, R₃ and R₁₃ each, independently of the other, are hydrogen atomsor alkyl groups, R₄ and R₁₄ each, independently of the other, arehydrogen atoms, fluorine atoms, alkyl groups, or phenyl groups, n is aninteger of 0, 1, 2, 3, or 4, and R₅ is an alkyl, aryl, arylalkyl, oralkylaryl group, or a substituent other than an alkyl, aryl, arylalkyl,or alkylaryl group, provided that at least one of R₁, R₁₁, R₂, R₁₂, R₃,R₁₃, R₄, R₁₄, or one or more of R₅ is an alkyl, alkylene, arylalkyl,arylalkylene, alkylaryl, or alkylarylene group containing an ethylenicunsaturation rendering the compound curable upon exposure to heat and/oractinic radiation.

Copending Application U.S. Ser. No. 11/181,632, filed Jul. 13, 2005,entitled “Ink Carriers, Phase Change Inks Including Same and Methods forMaking Same,” with the named inventors Adela Goredema, Christine E.Bedford, Marcel P. Breton, and Chris A. Wagner, the disclosure of whichis totally incorporated herein by reference, discloses an ink carriercomprising an ester terminated oligo-amide material having asubstantially low polydispersity. This ink carrier can be combined witha colorant to produce an ink composition.

Copending Application U.S. Ser. No. (not yet assigned; Attorney DocketNo. 20030890-US-NP), filed concurrently herewith, entitled “Phase ChangeInks Containing Curable Isocyanate-Derived Compounds,” with the namedinventors Jeffery H. Banning, Jennifer L. Belelie, Peter G. Odell, RinaCarlini, Jule W. Thomas, Donald R. Titterington, Paul F. Smith, StephanV. Drappel, and Christopher A. Wagner, the disclosure of which istotally incorporated herein by reference, discloses a phase change inkcomprising a colorant, an initiator, and a phase change ink carrier,said carrier comprising (A) a urethane which is the reaction product ofa mixture comprising (1) an isocyanate; and (2) an alcohol selected fromthe group consisting of 1,4 butanediol vinyl ether, 2-allyloxy ethanol,1,4-cyclohexanedimethanol vinyl ether, ethylene glycol vinyl ether,di(ethylene glycol) vinyl ether, and mixtures thereof; (B) a compoundwhich is the reaction product of a mixture comprising (1) an isocyanate;and (2) a component comprising (a) an amine having at least oneethylenic unsaturation; (b) an acid having at least one ethylenicunsaturation; (c) a mixture of an amine having at least one ethylenicunsaturation and an alcohol having at least one ethylenic unsaturation;(d) a mixture of an acid having at least one ethylenic unsaturation andan alcohol having at least one ethylenic unsaturation; or (e) mixturesthereof; or (C) a mixture of (A) and (B); said ink being curable uponexposure to ultraviolet radiation.

Copending Application U.S. Ser. No. (not yet assigned; Attorney DocketNo. 20031170-US-NP), filed concurrently herewith, entitled “Phase ChangeInks Containing Curable Isocyanate-Derived Compounds and Phase ChangeInducing Components,” with the named inventors Jennifer L. Belelie,Peter G. Odell, Marcel P. Breton, Jeffery H. Banning, Stephan V.Drappel, and Christopher A. Wagner, the disclosure of which is totallyincorporated herein by reference, discloses a phase change inkcomprising a colorant, an initiator, and a phase change ink carrier,said carrier comprising (A) a compound which is the reaction product ofa mixture comprising (1) an isocyanate; and (2) a component comprising(a) an alcohol having at least one ethylenic unsaturation; (b) an aminehaving at least one ethylenic unsaturation; (c) an acid having at leastone ethylenic unsaturation; or (d) mixtures thereof, (B) a phase changeinducing component, said phase change inducing component containing atleast one hydroxyl group, said phase change inducing component having amelting point of about 40° C. or higher, and (C) an optional curableviscosity modifying ester, said ink being curable upon exposure toultraviolet radiation.

Copending Application U.S. Ser. No. (not yet assigned; Attorney DocketNo. 20032040-US-NP), filed concurrently herewith, entitled “Phase ChangeInks Containing Compounds Derived from Isocyanate, Unsaturated Alcohol,and Polyol,” with the named inventors Jennifer L. Belelie, Rina Carlini,and Eniko Toma, the disclosure of which is totally incorporated hereinby reference, discloses a phase change ink comprising a colorant, aninitiator, and a phase change ink carrier, said carrier comprising (A) afirst isocyanate-derived compound which is the reaction product of amixture comprising (1) an isocyanate; and (2) a component comprising (a)an alcohol having at least one ethylenic unsaturation; (b) an aminehaving at least one ethylenic unsaturation; (c) an acid having at leastone ethylenic unsaturation; or (d) mixtures thereof, (B) a secondisocyanate-derived compound which is the reaction product of (1) adiisocyanate; (2) a monoalcohol having exactly one hydroxyl group andhaving at least one ethylenic unsaturation; and (3) a polyol having twoor more hydroxyl groups, (C) an optional phase change inducingcomponent, said phase change inducing component containing at least onehydroxyl group, said phase change inducing component having a meltingpoint of about 40° C. or higher, and (D) an optional curable viscositymodifying ester, said ink being curable upon exposure to ultravioletradiation.

Copending Application U.S. Ser. No. (not yet assigned; Attorney DocketNo. 20031091-US-NP), filed concurrently herewith, entitled “RadiationCurable Phase Change Inks Containing Curable Epoxy-Polyamide CompositeGellants,” with the named inventors Rina Carlini, Eniko Toma, Peter G.Odell, and Vaisnavi Siritharan, the disclosure of which is totallyincorporated herein by reference, discloses a radiation curable phasechange ink preferably used in piezoelectric ink jet devices including anink vehicle that includes at least one curable epoxy-polyamide gellant,and at least one colorant. The use of the gellant enables the ink toform a gel state having a viscosity of at least 10³ mPa·s at very lowtemperatures of about 25° C. to about 100° C. The ink may thus bejetted, for example onto an intermediate transfer member surface ordirectly to an image receiving substrate, at very low jettingtemperatures of, for example, about 40° C. to about 110° C. In apreferred method of forming an image with the ink, the ink is heated toa first temperature at which the ink may be jetted, jetted onto an imagereceiving or intermediate transfer member surface maintained at a secondtemperature at which the ink forms a gel state, if appropriatesubsequently transferred from the intermediate transfer member surfaceto an image receiving substrate, and exposed to radiation energy to curethe curable components of the ink.

Copending Application U.S. Ser. No. (not yet assigned; Attorney DocketNo. 20030937-US-NP), filed concurrently herewith, entitled “RadiationCurable Phase Change Inks Containing Gellants,” with the named inventorsPeter G. Odell, C. Geoffrey Allen, Christopher A. Wagner, Stephan V.Drappel, Rina Carlini, and Eniko Toma, the disclosure of which istotally incorporated herein by reference, discloses a radiation curablephase change ink preferably used in piezoelectric ink jet devicesincluding an ink vehicle that includes at least one gellant comprising acurable polyamide-epoxy acrylate component and a polyamide component,and at least one colorant. The use of the gellant enables the ink toform a gel state having a viscosity of at least 10³ mPa·s at very lowtemperatures of about 25° C. to about 100° C. The ink may thus be jettedat very low jetting temperatures of, for example, about 40° C. to about110° C. The ink may be used to form an image by heating the ink to afirst temperature at which the ink may be jetted, jetting onto a memberor substrate maintained at a second temperature at which the ink forms agel state, and exposing the ink to radiation energy to polymerizecurable components of the ink.

Copending Application U.S. Ser. No. (not yet assigned; Attorney DocketNo. 20041475-US-NP), filed concurrently herewith, entitled “Phase ChangeInks,” with the named inventors Peter Gordon Odell, Paul F. Smith,Jennifer Lynne Belelie, Eniko Toma, Stephan Drappel, C. Geoffrey Allen,Rina Carlini, and Christopher A. Wagner, the disclosure of which istotally incorporated herein by reference, discloses a phase change inkhaving a viscosity of from about 4 mPa·s to about 50 mPa·s at a firsttemperature and a viscosity of from 104 mPa·s to about 10⁹ mPa·s at asecond lower temperature. The second temperature may be below the firsttemperature by at least 10° C., but by no more than 50° C. The firsttemperature may be from about 60° C. to about 110° C. and the secondtemperature may be from about 20° C. to about 70° C. A curve of log₁₀viscosity of the phase change ink plotted against temperature in degreesCelsius may have a slope having an absolute value less than 0.02 at thefirst temperature and have a slope having an absolute value greater than0.08 for at least a region between the first and second temperatures.

Copending Application U.S. Ser. No. (not yet assigned; Attorney DocketNo. A3385-US-NP), filed concurrently herewith, entitled “Phase ChangeInks and Methods for Making Same,” with the named inventors AdelaGoredema, Christine E. Bedford, Marcel P. Breton, and Christopher A.Wagner, the disclosure of which is totally incorporated herein byreference, discloses a phase change ink composition and a method forforming the ink composition. The phase change ink composition comprises(1) an ink carrier comprising (A) a first component which comprises amonoester wax or blend of monoesters having at least one alkyl groupcomprising at least 10 carbon atoms, and (B) a second component whichcomprises a polyalkylene wax, and (2) a urea gellant, and (3) acolorant.

Copending Application U.S. Ser. No. (not yet assigned; Attorney DocketNo. A3595-US-NP), filed concurrently herewith, entitled “Ink CarriersContaining Nanoparticles, Phase Change Inks Including Same and Methodsfor Making Same,” with the named inventors Marcel P. Breton, AdelaGoredema, Christine E. Bedford, Christopher A. Wagner, Sandra Gardner,Nan-Xing Hu, and Bruce Goodbrand, the disclosure of which is totallyincorporated herein by reference, discloses an ink carrier and a methodfor forming same, and a phase change ink including same. The ink carriercomprises a colloidal dispersion of at least one of silica nanoparticlesand metal oxide particles. The ink carrier can also include a lowmelting wax, and a gelling agent. The ink carrier exhibits asubstantially uniform distribution of the nanoparticles so that they arediscretely distributed therewithin, and are substantially resistant tothe aggregation of the nanoparticles distributed therewith in.

Copending Application U.S. Ser. No. (not yet assigned; Attorney DocketNo. A3386-US-NP), filed concurrently herewith, entitled “Black Inks andMethod for Making Same,” with the named inventors Marcel P. Breton,Raymond W. Wong, Christine E. Bedford, Christopher A. Wagner, andCaroline Turek, the disclosure of which is totally incorporated hereinby reference, discloses a phase change black ink composition comprising(1) a low polarity ink carrier comprising (A) an ester-terminatedpolyamide, (B) a Guerbet alcohol or a Guerbet alcohol mixture containingat least one linear alcohol, and (C) a low polarity wax, and (2) a blackcolorant. The ink carrier can also contain a dispersant. The ink isresistant to aggregation and settling of the black colorant when astandby-mode printer temperature for the ink is not more than about thegel temperature of the ink.

Copending Application U.S. Ser. No. (not yet assigned; Attorney DocketNo. 20040313-US-NP), filed concurrently herewith, entitled “InkCarriers, Phase Change Inks Including Same and Methods for Making Same,”with the named inventors Marcel P. Breton, Adela Goredema, Christine E.Bedford, Christopher A. Wagner, Stephan Drappel, Caroline Turek, RaymondW. Wong, and Nadia Edun, the disclosure of which is totally incorporatedherein by reference, discloses an ink carrier comprising (A) anantioxidant mixture comprising (a) a hindered phenol antioxidant, and(b) a hindered amine antioxidant, (B) a polyalkylene wax, (C) afunctional wax, and (D) an ester-terminated amide. The low polarity inkcarrier is substantially resistant to phase separation, has excellentthermal stability, resists autocatalytic degradation of the inkcomposition and a substantial color shift upon standing, and providesenhanced humidity resistance. This ink carrier can be combined with acolorant to produce an ink composition.

Copending Application U.S. Ser. No. (not yet assigned; Attorney DocketNo. 20041459-US-NP), filed concurrently herewith, entitled “CurableOvercoat for Wax-Based Inks,” with the named inventors Jennifer L.Belelie and Peter G. Odell, the disclosure of which is totallyincorporated herein by reference, discloses an ink jettable overprintcomposition including at least one of a polymerizable monomer and/or apolymerizable oligomer; at least one photoinitiator; and at least onewax.

Copending Application U.S. Ser. No. (not yet assigned; Attorney DocketNo. 20040976-US-NP), filed concurrently herewith, entitled “RadiationCurable Ink Containing a Curable Wax,” with the named inventors JenniferLynne Belelie, Peter Gordon Odell, Christopher A. Wagner, and C.Geoffrey Allen, the disclosure of which is totally incorporated hereinby reference, discloses a curable monomer that is liquid at 25° C., acurable wax, and a colorant together forming a radiation curable ink.This ink may be used to form images by providing the radiation curableink at a first temperature; applying the radiation curable ink to thesubstrate to form an image, the substrate being at a second temperature,which is below the first temperature; and exposing the radiation curableink to radiation to cure the ink.

Copending Application U.S. Ser. No. (not yet assigned; Attorney DocketNo. 20040221-US-NP), filed concurrently herewith, entitled “CurablePhase Change Compositions and Methods for Using Such Compositions,” withthe named inventors Jennifer L. Belelie, Peter G. Odell, DarylVanbesien, and Marcel P. Breton, the disclosure of which is totallyincorporated herein by reference, discloses a phase change, curablecomposition comprising curable monomer, photoinitiator that initiatespolymerization of the curable monomer, and phase change agent thatprovides the composition with an increase in viscosity of at least fourorders of magnitude, from a first temperature, the first temperaturebeing from 50° C. to 130° C., to a second temperature, the secondtemperature being from 0° C. to 70° C., wherein the second temperatureis at least 10° C. below the first temperature. A coating over an imagemay be applied by providing a composition comprising curable monomer ata first temperature; applying the composition over the image, the imagebeing at a second temperature; and exposing the composition to radiationto initiate polymerization of the curable monomer. In this process, thecomposition has a viscosity at the second temperature that is at leastfour orders of magnitude greater than its viscosity at the firsttemperature.

Copending Application U.S. Ser. No. (not yet assigned; Attorney DocketNo. 20031933-US-NP), filed concurrently herewith, entitled “OvercoatCompositions, Oil-Based Ink Compositions, and Processes for Ink-JetRecording Using Overcoat Compositions and Oil-Based Ink Compositions,”with the named inventors Gregory J. Kovacs and Marcel P. Breton, thedisclosure of which is totally incorporated herein by reference,discloses overcoat compositions including film-forming resins andorganic liquids. Overcoat compositions are included in ink sets thatalso include oil-based ink compositions. Methods for ink-jet printinguse oil-based ink compositions and overcoat compositions.

Copending Application U.S. Ser. No. (not yet assigned; Attorney DocketNo. 20031777-US-NP), filed concurrently herewith, entitled“Pre-Treatment Compositions, Oil-Based Ink Compositions, and Processesfor Ink-Jet Recording Using Pre-Treatment Compositions and Oil-Based InkCompositions,” with the named inventors Gregory J. Kovacs and Marcel P.Breton, the disclosure of which is totally incorporated herein byreference, discloses pre-treatment compositions including organicliquids and cross-linking initiators. Pre-treatment compositions areincluded in ink sets that also include oil-based ink compositions.Oil-based ink compositions include organic liquids, unsaturated fattymaterials having terminal polar functional groups, colorants, and metalsalts. Methods for ink-jet printing use pre-treatment compositions andoil-based ink compositions.

Copending Application U.S. Ser. No. (not yet assigned; Attorney DocketNo. 20041415-US-NP), filed concurrently herewith, entitled“Photoinitiator With Phase Change Properties and Gellant Affinity,” withthe named inventors Peter G. Odell, Eniko Toma, and Jennifer L. Belelie,the disclosure of which is totally incorporated herein by reference,discloses a compound of the formula

wherein R₁ is an alkylene, arylene, arylalkylene, or alkylarylene group,R₂ and R₂′ each, independently of the other, are alkylene, arylene,arylalkylene, or alkylarylene groups, R₃ and R₃′ each, independently ofthe other, are either (a) photoinitiating groups, or (b) groups whichare alkyl, aryl, arylalkyl, or alkylaryl groups, provided that at leastone of R₃ and R₃′ is a photoinitiating group, and X and X′ each,independently of the other, is an oxygen atom or a group of the formula—NR₄—, wherein R₄ is a hydrogen atom, an alkyl group, an aryl group, anarylalkyl group, or an alkylaryl group.

Copending Application U.S. Ser. No. (not yet assigned; Attorney DocketNo. 20041415Q-US-NP), filed concurrently herewith, entitled “PhaseChange Inks Containing Photoinitiator With Phase Change Properties andGellant Affinity,” with the named inventors Peter G. Odell, Eniko Toma,and Jennifer L. Belelie, the disclosure of which is totally incorporatedherein by reference, discloses a phase change ink comprising a colorantand an ink vehicle, said ink vehicle comprising (a) at least oneradically curable monomer compound, and (b) a compound of the formula

wherein R₁ is an alkylene, arylene, arylalkylene, or alkylarylene group,R₂ and R₂′ each, independently of the other, are alkylene, arylene,arylalkylene, or alkylarylene groups, R₃ and R₃′ each, independently ofthe other, are either (a) photoinitiating groups, or (b) groups whichare alkyl, aryl, arylalkyl, or alkylaryl groups, provided that at leastone of R₃ and R₃′ is a photoinitiating group, and X and X′ each,independently of the other, is an oxygen atom or a group of the formula—NR₄—, wherein R₄ is a hydrogen atom, an alkyl group, an aryl group, anarylalkyl group, or an alkylaryl group.

Copending Application U.S. Ser. No. (not yet assigned; Attorney DocketNo. 20040531-US-NP), filed concurrently herewith, entitled “CurableAmide Gellant Compounds,” with the named inventors Eniko Toma, Peter G.Odell, Adela Goredema, and Jennifer L. Belelie, the disclosure of whichis totally incorporated herein by reference, discloses a compound of theformula

wherein R₁ and R₁′ each, independently of the other, is an alkyl grouphaving at least one ethylenic unsaturation, an arylalkyl group having atleast one ethylenic unsaturation, or an alkylaryl group having at leastone ethylenic unsaturation, R₂, R₂′, and R₃ each, independently of theothers, are alkylene groups, arylene groups, arylalkylene groups, oralkylarylene groups, and n is an integer representing the number ofrepeat amide units and is at least 1.

Copending Application U.S. Ser. No. (not yet assigned; Attorney DocketNo. 20040531Q1-US-NP), filed concurrently herewith, entitled “Processfor Making Curable Amide Gellant Compounds,” with the named inventorsEniko Toma, Adela Goredema, Jennifer L. Belelie, and Peter G. Odell, thedisclosure of which is totally incorporated herein by reference,discloses a process for preparing a compound of the formula

wherein R₁ is an alkyl group having at least one ethylenic unsaturation,an arylalkyl group having at least one ethylenic unsaturation, or analkylaryl group having at least one ethylenic unsaturation, R₂ and R₃each, independently of the others, are alkylene groups, arylene groups,arylalkylene groups, or alkylarylene groups, and n is an integerrepresenting the number of repeat amide units and is at least 1, saidprocess comprising: (a) reacting a diacid of the formulaHOOC—R₂—COOHwith a diamine of the formula

in the presence of a catalyst, a solvent, and a coupling agent to forman oligoamide intermediate of the formula

and (b) reacting the oligoamide intermediate with an alcohol of theformulaR₁—OHto form the product.

Copending Application U.S. Ser. No. (not yet assigned; Attorney DocketNo. 20041514-US-NP), filed concurrently herewith, entitled “Method forPreparing Curable Amide Gellant Compounds,” with the named inventorsJennifer L. Belelie, Adela Goredema, Peter G. Odell, and Eniko Toma, thedisclosure of which is totally incorporated herein by reference,discloses a process for preparing a compound of the formula

wherein R₁ is an alkyl group having at least one ethylenic unsaturation,an arylalkyl group having at least one ethylenic unsaturation, or analkylaryl group having at least one ethylenic unsaturation, R₂ and R₃each, independently of the others, are alkylene groups, arylene groups,arylalkylene groups, or alkylarylene groups, and n is an integerrepresenting the number of repeat amide units and is at least 1, saidprocess comprising: (a) reacting a diacid of the formulaHOOC—R₂—COOHwith a diamine of the formula

in the absence of a solvent while removing water from the reactionmixture to form an acid-terminated oligoamide intermediate; and (b)reacting the acid-terminated oligoamide intermediate with a monoalcoholof the formulaR₁—OHin the presence of a coupling agent and a catalyst to form the product.

BACKGROUND

Disclosed herein are curable ester-terminated oligoamide compounds andink compositions containing them. One embodiment disclosed herein isdirected to a phase change ink comprising a colorant, an initiator, anda phase change ink carrier, said carrier comprising at least oneradically curable monomer compound and a compound of the formula

wherein R₁ and R₁′ each, independently of the other, is (i) an alkylgroup having at least one ethylenic unsaturation therein (includinglinear and branched, cyclic and acyclic, and substituted andunsubstituted alkyl groups, and wherein hetero atoms either may or maynot be present in the alkyl group), (ii) an arylalkyl group having atleast one ethylenic unsaturation therein (including substituted andunsubstituted arylalkyl groups, wherein the alkyl portion of thearylalkyl group can be linear or branched, cyclic or acyclic, andsubstituted or unsubstituted, and wherein hetero atoms either may or maynot be present in either the aryl or the alkyl portion of the arylalkylgroup), or (iii) an alkylaryl group having at least one ethylenicunsaturation therein (including substituted and unsubstituted alkylarylgroups, wherein the alkyl portion of the alkylaryl group can be linearor branched, cyclic or acyclic, and substituted or unsubstituted, andwherein hetero atoms either may or may not be present in either the arylor the alkyl portion of the alkylaryl group), R₂, R₂′, and R₃ each,independently of the others, are (i) alkylene groups, including linearand branched, saturated and unsaturated, cyclic and acyclic, andsubstituted and unsubstituted alkylene groups, and wherein hetero atomseither may or may not be present in the alkylene group, (ii) arylenegroups, including substituted and unsubstituted arylene groups, andwherein hetero atoms either may or may not be present in the arylenegroup, (iii) arylalkylene groups, including substituted andunsubstituted arylalkylene groups, wherein the alkyl portion of thearylalkylene group can be linear or branched, saturated or unsaturated,cyclic or acyclic, and substituted or unsubstituted, and wherein heteroatoms either may or may not be present in either the aryl or the alkylportion of the arylalkylene group, or (iv) alkylarylene groups,including substituted and unsubstituted alkylarylene groups, wherein thealkyl portion of the alkylarylene group can be linear or branched,saturated or unsaturated, cyclic or acyclic, and substituted orunsubstituted, and wherein hetero atoms either may or may not be presentin either the aryl or the alkyl portion of the alkylarylene group, and nis an integer representing the number of repeat amide units and is atleast 1.

In general, phase change inks (sometimes referred to as “hot melt inks”)are in the solid phase at ambient temperature, but exist in the liquidphase at the elevated operating temperature of an ink jet printingdevice. At the jet operating temperature, droplets of liquid ink areejected from the printing device and, when the ink droplets contact thesurface of the recording substrate, either directly or via anintermediate heated transfer belt or drum, they quickly solidify to forma predetermined pattern of solidified ink drops. Phase change inks havealso been used in other printing technologies, such as gravure printing,as disclosed in, for example, U.S. Pat. No. 5,496,879 and German PatentPublications DE 4205636AL and DE 4205713AL, the disclosures of each ofwhich are totally incorporated herein by reference.

Phase change inks for color printing typically comprise a phase changeink carrier composition which is combined with a phase change inkcompatible colorant. In a specific embodiment, a series of colored phasechange inks can be formed by combining ink carrier compositions withcompatible subtractive primary colorants. The subtractive primarycolored phase change inks can comprise four component dyes, namely,cyan, magenta, yellow and black, although the inks are not limited tothese four colors. These subtractive primary colored inks can be formedby using a single dye or a mixture of dyes. For example, magenta can beobtained by using a mixture of Solvent Red Dyes or a composite black canbe obtained by mixing several dyes. U.S. Pat. No. 4,889,560, U.S. Pat.No. 4,889,761, and U.S. Pat. No. 5,372,852, the disclosures of each ofwhich are totally incorporated herein by reference, teach that thesubtractive primary colorants employed can comprise dyes from theclasses of Color Index (C.I.) Solvent Dyes, Disperse Dyes, modified Acidand Direct Dyes, and Basic Dyes. The colorants can also includepigments, as disclosed in, for example, U.S. Pat. No. 5,221,335, thedisclosure of which is totally incorporated herein by reference. U.S.Pat. No. 5,621,022, the disclosure of which is totally incorporatedherein by reference, discloses the use of a specific class of polymericdyes in phase change ink compositions.

Phase change inks have also been used for applications such as postalmarking, industrial marking, and labelling.

Phase change inks are desirable for ink jet printers because they remainin a solid phase at room temperature during shipping, long term storage,and the like. In addition, the problems associated with nozzle cloggingas a result of ink evaporation with liquid ink jet inks are largelyeliminated, thereby improving the reliability of the ink jet printing.Further, in phase change ink jet printers wherein the ink droplets areapplied directly onto the final recording substrate (for example, paper,transparency material, and the like), the droplets solidify immediatelyupon contact with the substrate, so that migration of ink along theprinting medium is prevented and dot quality is improved.

Compositions suitable for use as phase change ink carrier compositionsare known. Some representative examples of references disclosing suchmaterials include U.S. Pat. No. 3,653,932, U.S. Pat. No. 4,390,369, U.S.Pat. No. 4,484,948, U.S. Pat. No. 4,684,956, U.S. Pat. No. 4,851,045,U.S. Pat. No. 4,889,560, U.S. Pat. No. 5,006,170, U.S. Pat. No.5,151,120, U.S. Pat. No. 5,372,852, U.S. Pat. No. 5,496,879, EuropeanPatent Publication 0187352, European Patent Publication 0206286, GermanPatent Publication DE 4205636AL, German Patent Publication DE 4205713AL,and PCT Patent Application WO 94/04619, the disclosures of each of whichare totally incorporated herein by reference. Suitable carrier materialscan include paraffins, microcrystalline waxes, polyethylene waxes, esterwaxes, fatty acids and other waxy materials, fatty amide containingmaterials, sulfonamide materials, resinous materials made from differentnatural sources (tall oil rosins and rosin esters, for example), andmany synthetic resins, oligomers, polymers, and copolymers.

U.S. Pat. No. 5,804,671 (Dones et al.), the disclosure of which istotally incorporated herein by reference, discloses a composition thatis useful in the preparation of radiation curable coatings. Thecomposition comprises the reaction product of an epoxy componentcomprising a diepoxide and an acid component comprising an ethylenicallyunsaturated carboxylic acid or reactive derivative thereof, reacted inthe presence of a polyamide based on a polymerized fatty acid. Thepolyamide preferably has a number average molecular weight of less thanabout 10,000 g/mole. Also provided is a polymerizable compositioncomprising the reaction product and a reactive diluent. A method ofcoating a substrate is also provided which comprises applying to asubstrate a composition comprising the reaction product and exposingsaid composition to radiation to cure said composition.

U.S. Pat. No. 5,889,076 (Dones et al.), the disclosure of which istotally incorporated herein by reference, discloses a composition thatis useful in the preparation of radiation curable coatings. Thecomposition comprises the reaction product of an epoxy component and anacid component comprising an ethylenically unsaturated carboxylic acidor reactive derivative thereof, reacted in the presence of, orpost-reaction blended with, a polyamide based on a polymerized fattyacid. The polyamide preferably has a number average molecular weight ofless than about 10,000 g/mole. Also provided is a polymerizablecomposition comprising the reaction product, the polyamide, and areactive diluent. A method of coating a substrate is also provided whichcomprises applying to a substrate a composition comprising the reactionproduct and the polyamide and exposing said composition to radiation tocure said composition.

U.S. Pat. No. 6,239,189 (Narayan et al.), the disclosure of which istotally incorporated herein by reference, discloses aradiation-polymerizable composition containing at least one radiationcurable acrylate resin oligomer prepared by reacting an alkoxylatedpolyol with a first acid component which includes an ethylenicallyunsaturated carboxylic acid, and a rheology modifier prepared byreacting a diepoxide with a second acid component which includes anethylenically unsaturated carboxylic acid or reactive derivative thereofin the presence of a polyamide based on a polymerized fatty acid. Theethylenically unsaturated carboxylic acids of the first and second acidcomponents are preferably acrylic acid or methacrylic acids. Thediepoxide is preferably a diglycidyl ether such as bisphenol A.Colorants such as pigments or dyes optionally may be incorporated intothe composition to form a printing ink which is curable by ultraviolet(UV) or electron beam radiation.

U.S. Pat. No. 6,316,517 (Dones et al.), the disclosure of which istotally incorporated herein by reference, disclosesradiation-polymerizable compositions especially useful as or in a flushvehicle for making flushed pigments. The compositions contain at leastone radiation-curable acrylated resin component and a copolymerizablerheology modifier component.

U.S. patent Publication 2003/0036587 (Kozak), the disclosure of which istotally incorporated herein by reference, discloses rheology-controlledepoxy-based compositions particularly well suited for use in coatingapplications such as in the assembly of ink jet printheads for theprinting industry, and in the microelectronics industry such as in theassembly of semiconductor devices.

U.S. Pat. No. 6,586,492 (Caiger et al.), the disclosure of which istotally incorporated herein by reference, discloses an ink jet inkincluding an ink jet vehicle and a colorant. The vehicle includes atleast 35 percent by weight radiation curable material based on the totalvehicle weight. The vehicle may but does not necessarily include athickener. The vehicle is a paste or a solid at 20° C. and has aviscosity of less than 25 centipoise between 40° C. and 130° C.

U.S. Pat. No. 6,467,897 (Wu et al.), the disclosure of which is totallyincorporated herein by reference, discloses compositions thatincorporate surface modified, nanometer sized, inorganic oxide particlesinto energy curable fluids. The surface modification aspect allows thecompatibility between the particles and fluid to be controllablyadjusted to achieve a wide range of rheological characteristics. Forprinting, preferred compositions have favorable dot gain and thicknessbuild up. When the composition is cured, the presence of the particlesalso helps improve physical properties such as hardness, modulus,abrasion resistance, refractive index, and the like. The compositionsare particularly well-suited for forming printed, radiation curedfeatures on substrates such as paper, signs, walkways, roadways, motorvehicles, boats, aircraft, furniture, equipment, and the like.

U.S. Pat. No. 6,896,937 (Woudenberg), the disclosure of which is totallyincorporated herein by reference, discloses radiation-curable inkcompositions and methods of printing including the compositions. In someembodiments, a radiation-curable hot melt ink composition includes acolorant, a polymerizable monomer, and a photoinitiating system. Thephotoinitiating system can include 0.5 to 1.5 percent by weight of anaromatic ketone photoinitiator, 2 to 10 percent by weight of an aminesynergist, 3 to 8 percent by weight of an alpha-cleavage typephotoinitiator, and 0.5 to 1.5 percent by weight of a photosensitizer.

While known compositions and processes are suitable for their intendedpurposes, a need remains for improved phase change ink compositions. Inaddition, a need remains for phase change inks that produce images withimproved scratch resistance. Further, a need remains for phase changeinks that produce images with improved adhesion to substrates such aspaper. Additionally, a need remains for ultraviolet curable compoundsthat are soluble in phase change ink carriers. There is also a need forultraviolet curable compounds that can be incorporated into phase changeink carriers without adversely affecting the viscosity characteristicsof the ink at desired jetting temperatures. In addition, there is a needfor ultraviolet curable compounds that can be incorporated into phasechange ink carriers without adversely affecting the melting point of theink. Further, there is a need for ultraviolet curable phase change inksthat can be used in ink jet printing processes wherein the ink is firstjetted onto an intermediate transfer member and subsequently transferredfrom the transfer member to a final substrate such as paper ortransparency material. Additionally, there is a need for ultravioletcurable phase change inks that can be used in ink jet printing processeswherein the ink is jetted directly onto a final substrate such as paperor transparency material. A need also remains for phase change inks thatgenerate images that exhibit improved robustness on the final recordingsheet. In addition, a need remains for phase change inks that generateimages with improved toughness. Further, a need remains for phase changeinks that can be jetted at reduced temperatures. Additionally, a needremains for phase change inks that enable control of dot spread of theink, particularly in processes wherein the ink is jetted directly onto afinal substrate. There is also a need for phase change inks that enableproduction of images that exhibit improved archival color properties. Inaddition, there is a need for phase change inks wherein the ink does notbleed excessively into the substrate, particularly in processes whereinthe ink is jetted directly onto a final substrate. Further, there is aneed for phase change inks wherein the ink does not generate anundesirably high pile height and wherein an unnecessarily high number ofdrops are needed to create the image, particularly in processes whereinthe ink is jetted directly onto a final substrate. Additionally, thereis a need for phase change inks wherein the ink generates images withreduced showthrough. A need also remains for phase change inks whereinthe increased viscosity of the ink during photoinitiation reduces therate of diffusion of oxygen and its inhibitory effect in the ink,thereby increasing the efficiency of cure.

SUMMARY

Disclosed herein is a phase change ink comprising a colorant, aninitiator, and a phase change ink carrier, said carrier comprising atleast one radically curable monomer compound and a compound of theformula

wherein R₁ and R₁′ each, independently of the other, is (i) an alkylgroup having at least one ethylenic unsaturation therein (includinglinear and branched, cyclic and acyclic, and substituted andunsubstituted alkyl groups, and wherein hetero atoms either may or maynot be present in the alkyl group), (ii) an arylalkyl group having atleast one ethylenic unsaturation therein (including substituted andunsubstituted arylalkyl groups, wherein the alkyl portion of thearylalkyl group can be linear or branched, cyclic or acyclic, andsubstituted or unsubstituted, and wherein hetero atoms either may or maynot be present in either the aryl or the alkyl portion of the arylalkylgroup), or (iii) an alkylaryl group having at least one ethylenicunsaturation therein (including substituted and unsubstituted alkylarylgroups, wherein the alkyl portion of the alkylaryl group can be linearor branched, cyclic or acyclic, and substituted or unsubstituted, andwherein hetero atoms either may or may not be present in either the arylor the alkyl portion of the alkylaryl group), R₂, R₂′, and R₃ each,independently of the others, are (i) alkylene groups, including linearand branched, saturated and unsaturated, cyclic and acyclic, andsubstituted and unsubstituted alkylene groups, and wherein hetero atomseither may or may not be present in the alkylene group, (ii) arylenegroups, including substituted and unsubstituted arylene groups, andwherein hetero atoms either may or may not be present in the arylenegroup, (iii) arylalkylene groups, including substituted andunsubstituted arylalkylene groups, wherein the alkyl portion of thearylalkylene group can be linear or branched, saturated or unsaturated,cyclic or acyclic, and substituted or unsubstituted, and wherein heteroatoms either may or may not be present in either the aryl or the alkylportion of the arylalkylene group, or (iv) alkylarylene groups,including substituted and unsubstituted alkylarylene groups, wherein thealkyl portion of the alkylarylene group can be linear or branched,saturated or unsaturated, cyclic or acyclic, and substituted orunsubstituted, and wherein hetero atoms either may or may not be presentin either the aryl or the alkyl portion of the alkylarylene group, and nis an integer representing the number of repeat amide units and is atleast 1.

DETAILED DESCRIPTION

The compounds disclosed herein are of the formula

wherein:

R₁ and R₁′ each, independently of the other, is:

(i) an alkyl group having at least one ethylenic unsaturation therein(including linear and branched, cyclic and acyclic, and substituted andunsubstituted alkyl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, boron, and the like either may ormay not be present in the alkyl group), in one embodiment with at leastabout 2 carbon atoms, in another embodiment with at least about 3 carbonatoms, and in yet another embodiment with at least about 4 carbon atoms,and in one embodiment with no more than about 100 carbon atoms, inanother embodiment with no more than about 60 carbon atoms, and in yetanother embodiment with no more than about 30 carbon atoms, although thenumber of carbon atoms can be outside of these ranges,

(ii) an arylalkyl group having at least one ethylenic unsaturationtherein (including substituted and unsubstituted arylalkyl groups,wherein the alkyl portion of the arylalkyl group can be linear orbranched, cyclic or acyclic, and substituted or unsubstituted, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, boron, and the like either may or may not be present ineither the aryl or the alkyl portion of the arylalkyl group), in oneembodiment with at least about 6 carbon atoms, and in another embodimentwith at least about 7 carbon atoms, and in one embodiment with no morethan about 100 carbon atoms, in another embodiment with no more thanabout 60 carbon atoms, and in yet another embodiment with no more thanabout 30 carbon atoms, although the number of carbon atoms can beoutside of these ranges, such as benzyl or the like, or

(iii) an alkylaryl group having at least one ethylenic unsaturationtherein (including substituted and unsubstituted alkylaryl groups,wherein the alkyl portion of the alkylaryl group can be linear orbranched, cyclic or acyclic, and substituted or unsubstituted, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, boron, and the like either may or may not be present ineither the aryl or the alkyl portion of the alkylaryl group), in oneembodiment with at least about 6 carbon atoms, and in another embodimentwith at least about 7 carbon atoms, and in one embodiment with no morethan about 100 carbon atoms, in another embodiment with no more thanabout 60 carbon atoms, and in yet another embodiment with no more thanabout 30 carbon atoms, although the number of carbon atoms can beoutside of these ranges, such as tolyl or the like, wherein thesubstituents on the substituted alkyl, arylalkyl, and alkylaryl groupscan be (but are not limited to) halogen atoms, ether groups, aldehydegroups, ketone groups, ester groups, amide groups, carbonyl groups,thiocarbonyl groups, sulfate groups, sulfonate groups, sulfonic acidgroups, sulfide groups, sulfoxide groups, phosphine groups, phosphoniumgroups, phosphate groups, nitrile groups, mercapto groups, nitro groups,nitroso groups, sulfone groups, acyl groups, acid anhydride groups,azide groups, azo groups, cyanato groups, isocyanato groups, thiocyanatogroups, isothiocyanato groups, carboxylate groups, carboxylic acidgroups, urethane groups, urea groups, mixtures thereof, and the like,wherein two or more substituents can be joined together to form a ring;

R₂ and R₂′ each, independently of the other, are:

(i) alkylene groups (wherein an alkylene group is defined as a divalentaliphatic group or alkyl group, including linear and branched, saturatedand unsaturated, cyclic and acyclic, and substituted and unsubstitutedalkylene groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, boron, and the like either may or may notbe present in the alkylene group), in one embodiment with at least 2carbon atoms, in another embodiment with at least about 4 carbon atoms,in yet another embodiment with at least about 6 carbon atoms, in stillanother embodiment with at least about 8 carbon atoms, in anotherembodiment with at least about 10 carbon atoms, in yet anotherembodiment with at least about 12 carbon atoms, in still anotherembodiment with at least about 14 carbon atoms, in another embodimentwith at least about 16 carbon atoms, in yet another embodiment with atleast about 18 carbon atoms, in still another embodiment with at leastabout 20 carbon atoms, in another embodiment with at least about 22carbon atoms, in yet another embodiment with at least about 24 carbonatoms, in still another embodiment with at least about 26 carbon atoms,in another embodiment with at least about 28 carbon atoms, in yetanother embodiment with at least about 30 carbon atoms, in still anotherembodiment with at least about 32 carbon atoms, in another embodimentwith at least about 34 carbon atoms, and in yet another embodiment withat least about 36 carbon atoms, and in one embodiment with no more thanabout 100 carbon atoms, in another embodiment with no more than about 60carbon atoms, and in yet another embodiment with no more than about 50carbon atoms, although the number of carbon atoms can be outside ofthese ranges,

(ii) arylene groups (wherein an arylene group is defined as a divalentaromatic group or aryl group, including substituted and unsubstitutedarylene groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, boron, and the like either may or may notbe present in the arylene group), in one embodiment with at least about5 carbon atoms, and in another embodiment with at least about 6 carbonatoms, and in one embodiment with no more than about 100 carbon atoms,in another embodiment with no more than about 60 carbon atoms, and inyet another embodiment with no more than about 50 carbon atoms, althoughthe number of carbon atoms can be outside of these ranges,

(iii) arylalkylene groups (wherein an arylalkylene group is defined as adivalent arylalkyl group, including substituted and unsubstitutedarylalkylene groups, wherein the alkyl portion of the arylalkylene groupcan be linear or branched, saturated or unsaturated, cyclic or acyclic,and substituted or unsubstituted, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, boron, and the likeeither may or may not be present in either the aryl or the alkyl portionof the arylalkylene group), in one embodiment with at least about 6carbon atoms, and in another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 100 carbon atoms,in another embodiment with no more than about 60 carbon atoms, and inyet another embodiment with no more than about 50 carbon atoms, althoughthe number of carbon atoms can be outside of these ranges, or

(iv) alkylarylene groups (wherein an alkylarylene group is defined as adivalent alkylaryl group, including substituted and unsubstitutedalkylarylene groups, wherein the alkyl portion of the alkylarylene groupcan be linear or branched, saturated or unsaturated, cyclic or acyclic,and substituted or unsubstituted, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, boron, and the likeeither may or may not be present in either the aryl or the alkyl portionof the alkylarylene group), in one embodiment with at least about 6carbon atoms, and in another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 100 carbon atoms,in another embodiment with no more than about 60 carbon atoms, and inyet another embodiment with no more than about 50 carbon atoms, althoughthe number of carbon atoms can be outside of these ranges, wherein thesubstituents on the substituted alkylene, arylene, arylalkylene, andalkylarylene groups can be (but are not limited to) pyridine groups,pyridinium groups, ether groups, aldehyde groups, ketone groups, estergroups, amide groups, carbonyl groups, thiocarbonyl groups, sulfidegroups, phosphine groups, phosphonium groups, phosphate groups, nitrilegroups, mercapto groups, nitro groups, nitroso groups, acyl groups, acidanhydride groups, azide groups, azo groups, thiocyanato groups,carboxylate groups, urethane groups, urea groups, mixtures thereof, andthe like, wherein two or more substituents can be joined together toform a ring;

-   R₃ is:

(i) an alkylene group (wherein an alkylene group is defined as adivalent aliphatic group or alkyl group, including linear and branched,saturated and unsaturated, cyclic and acyclic, and substituted andunsubstituted alkylene groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, boron, and the like either may ormay not be present in the alkylene group), in one embodiment with atleast 2 carbon atoms, and in one embodiment with no more than about 80carbon atoms, in another embodiment with no more than about 60 carbonatoms, in yet another embodiment with no more than about 50 carbonatoms, and in still another embodiment with no more than about 36 carbonatoms, although the number of carbon atoms can be outside of theseranges,

(ii) an arylene group (wherein an arylene group is defined as a divalentaromatic group or aryl group, including substituted and unsubstitutedarylene groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, boron, and the like either may or may notbe present in the arylene group), in one embodiment with at least about5 carbon atoms, and in another embodiment with at least about 6 carbonatoms, and in one embodiment with no more than about 50 carbon atoms, inanother embodiment with no more than about 25 carbon atoms, and in yetanother embodiment with no more than about 18 carbon atoms, although thenumber of carbon atoms can be outside of these ranges,

(iii) an arylalkylene group (wherein an arylalkylene group is defined asa divalent arylalkyl group, including substituted and unsubstitutedarylalkylene groups, wherein the alkyl portion of the arylalkylene groupcan be linear or branched, saturated or unsaturated, cyclic or acyclic,and substituted or unsubstituted, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, boron, and the likeeither may or may not be present in either the aryl or the alkyl portionof the arylalkylene group), in one embodiment with at least about 6carbon atoms, and in another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 50 carbon atoms, inanother embodiment with no more than about 36 carbon atoms, and in yetanother embodiment with no more than about 18 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, or

(iv) an alkylarylene group (wherein an alkylarylene group is defined asa divalent alkylaryl group, including substituted and unsubstitutedalkylarylene groups, wherein the alkyl portion of the alkylarylene groupcan be linear or branched, saturated or unsaturated, cyclic or acyclic,and substituted or unsubstituted, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, boron, and the likeeither may or may not be present in either the aryl or the alkyl portionof the alkylarylene group), in one embodiment with at least about 6carbon atoms, and in another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 50 carbon atoms, inanother embodiment with no more than about 36 carbon atoms, and in yetanother embodiment with no more than about 18 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, wherein thesubstituents on the substituted alkylene, arylene, arylalkylene, andalkylarylene groups can be (but are not limited to) pyridine groups,pyridinium groups, ether groups, aldehyde groups, ketone groups, estergroups, amide groups, carbonyl groups, thiocarbonyl groups, sulfidegroups, phosphine groups, phosphonium groups, phosphate groups, nitrilegroups, mercapto groups, nitro groups, nitroso groups, acyl groups, acidanhydride groups, azide groups, azo groups, carboxylate groups, urethanegroups, urea groups, mixtures thereof, and the like, wherein two or moresubstituents can be joined together to form a ring;

and n is an integer representing the number of repeat amide units, beingin one embodiment at least 1, and in one embodiment no more than about20, in another embodiment no more than about 15, and in yet anotherembodiment no more than about 10, although the value of n can be outsideof these ranges.

In one specific embodiment, R₁ and R₁′ are the same as each other; inanother specific embodiment, R₁ and R₁′ are different from each other.In one specific embodiment, R₂ and R₂′ are the same as each other; inanother specific embodiment, R₂ and R₂′ are different from each other.In one specific embodiment, R₁ and R₁′ are the same as each other and R₂and R₂′ are the same as each other.

In one specific embodiment, R₁ and R₁′ are each of the formulaH₂C═CH—O—(CH₂)₄—

In another specific embodiment, R₁ and R₁′ are each of the formulaH₂C═CH—O—(CH₂)₂—O—(CH₂)₂—

In yet another specific embodiment, R₁ and R₁′ are each of the formula

In still another specific embodiment, R₁ and R₁′ are each of the formula

In another specific embodiment, R₁ and R₁′ are each of the formula

wherein m is an integer representing the number of repeating [O—(CH₂)₂]units, and is in one specific embodiment 2 and is in another specificembodiment 5.

In yet another specific embodiment, R₁ and R₁ are each of the formula

In one specific embodiment, R₂ and R₂′ are each groups of the formula—C₃₄H_(56+a)— and are branched alkylene groups which may includeunsaturations and cyclic groups, wherein a is an integer of 0, 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11, or 12, including (but not limited to) isomersof the formula

In one specific embodiment, R₃ is an ethylene (—CH₂CH₂—) group.

In one specific embodiment, n is 1 or 2.

In one specific embodiment, the compound is of the formula

wherein —C₃₄H_(56+a)— represents a branched alkylene group which mayinclude unsaturations and cyclic groups, wherein a is an integer of 0,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, including (but not limited to)isomers of the formula

wherein n is 1 or 2.

Additional specific examples of compounds of this formula include thoseof the formula

wherein —C₃₄H_(56+a)— represents a branched alkylene group which mayinclude unsaturations and cyclic groups, wherein a is an integer of 0,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, including (but not limited to)isomers of the formula

wherein n is 1 or 2, those of the formula

wherein —C₃₄H_(56+a)— represents a branched alkylene group which mayinclude unsaturations and cyclic groups, wherein a is an integer of 0,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, including (but not limited to)isomers of the formula

wherein n is 1 or 2, those of the formula

wherein —C₃₄H_(56+a)— represents a branched alkylene group which mayinclude unsaturations and cyclic groups, wherein a is an integer of 0,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, including (but not limited to)isomers of the formula

wherein n is 1 or 2, those of the formula

wherein —C₃₄H_(56+a)— represents a branched alkylene group which mayinclude unsaturations and cyclic groups, wherein a is an integer of 0,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, including (but not limited to)isomers of the formula

wherein n is 1 or 2, those of the formula

wherein —C₃₄H_(56+a)— represents a branched alkylene group which mayinclude unsaturations and cyclic groups, wherein a is an integer of 0,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, wherein m is an integerrepresenting the number of repeating [O—(CH₂)₂] units, and is in onespecific embodiment 2 and is in another specific embodiment 5, including(but not limited to) isomers of the formula

wherein n is 1 or 2, wherein m is an integer representing the number ofrepeating [O—(CH₂)₂] units, and is in one specific embodiment 2 and isin another specific embodiment 5, those of the formula

wherein —C₃₄H_(56+a)— represents a branched alkylene group which mayinclude unsaturations and cyclic groups, wherein a is an integer of 0,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, including (but not limited to)isomers of the formula

wherein n is 1 or 2, and the like, as well as mixtures thereof.

Compounds as disclosed herein can be prepared by any desired oreffective method. For example, in one specific embodiment, about 2 molarequivalents of a diacid of the formulaHOOC—R₂—COOHand about one molar equivalent of a diamine of the formula

can be reacted by use of a coupling agent such as1,3-dicyclohexylcarbodiimide (DCC) in the presence of a catalyst such as4-dimethylaminopyridine (DMAP) in the presence of a solvent such asmethylene chloride (CH₂Cl₂) at reduced temperatures followed by eventualwarming to about room temperature. To the resulting reaction mixture isadded about two molar equivalents of a monoalcohol of the formulaR₁—OHWhen n is 1, the ingredients can be mixed together in the sequence justdescribed and a one-pot reaction can be employed. When n is an oddnumber greater than 1, the reaction can proceed in a multistep processas follows:

wherein A is the coupling agent. When n is greater than 3 and an oddnumber, steps 2 and 3 can be repeated (n−3) times to obtain the desiredproduct. When n is greater than 1 and an even number, the reaction canproceed in a multistep process as follows:

wherein A is the coupling agent.

When n is an even number greater than 2, the compound of the formula

is reacted with 2 equivalents of the diamine, followed by 2 equivalentsof the diacid. This sequence can be repeated (n/2-1) times to obtain thedesired product. For example, if n is desired to be 4, the sequentialsteps would be repeated once to obtain a product wherein n is 4.

The diacid and the diamine in step 1 are present in any desired oreffective relative amounts, in one embodiment at least about 1.75 molesof diamine per every 1 mole of diacid, in another embodiment at leastabout 1.9 moles of diamine per every 1 mole of diacid, and in yetanother embodiment at least about 2 moles of diamine per every one moleof diacid, and in one embodiment no more than about 2.5 moles of diamineper every 1 mole of diacid, in another embodiment no more than about 2.3moles of diamine per every 1 mole of diacid, and in yet anotherembodiment no more than about 2.1 moles of diamine per every 1 mole ofdiacid, although the relative amounts can be outside of these ranges.

Reaction product (I) and the diacid in step 2 are present in any desiredor effective relative amounts, in one embodiment at least about 1.75moles of diacid per every one mole of reaction product (I), in anotherembodiment at least about 1.9 moles of diacid per every one mole ofreaction product (I), and in yet another embodiment at least about 2moles of diacid per every one mole of reaction product (I), and in oneembodiment no more than about 2.3 moles of diacid per every one mole ofreaction product (I), in another embodiment no more than about 2.2 molesof diacid per every one mole of reaction product (I), and in yet anotherembodiment no more than about 2.1 moles of diacid per every one mole ofreaction product (I), although the relative amounts can be outside ofthese ranges.

Reaction product (II) and the monoalcohol are present in any desired oreffective relative amounts, in one embodiment at least about 1.75 molesof monoalcohol per every one mole of reaction product (II), in anotherembodiment at least about 2 moles of monoalcohol per every one mole ofreaction product (II), and in yet another embodiment at least about 2.25moles of monoalcohol per every one mole of reaction product (II), and inone embodiment no more than about 3 moles of monoalcohol per every onemole of reaction product (II), in another embodiment no more than about2.75 moles of monoalcohol per every one mole of reaction product (II),and in yet another embodiment no more than about 2.5 moles ofmonoalcohol per every one mole of reaction product (II), although therelative amounts can be outside of these ranges.

When n=1, the diacid and the monoalcohol are present in any desired oreffective relative amounts, in one embodiment at least about 0.75 moleof monoalcohol per every 1 mole of diacid, in another embodiment atleast about 1 mole of monoalcohol per every 1 mole of diacid, and in yetanother embodiment at least about 1.25 moles of monoalcohol per everyone mole of diacid, and in one embodiment no more than about 2 moles ofmonoalcohol per every 1 mole of diacid, in another embodiment no morethan about 1.75 moles of monoalcohol per every 1 mole of diacid, and inyet another embodiment no more than about 1.5 moles of monoalcohol perevery 1 mole of diacid, although the relative amounts can be outside ofthese ranges.

Examples of suitable coupling agents include1,3-dicyclohexylcarbodiimide (DCC), of the formula

1-[3-(dimethylamino)propyl] 3-ethylcarbodiimide HCl (EDCI),N,N-carbonyldiimidazole,N-cyclohexyl-N′-(2-morpholinoethyl)-carbodiimidemethyl-p-toluenesulfonate,(benzotriazol-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate(BOP), (obenzotriazol-1-yl)-N,N,N′,N′-bis(tetramethylene)uroniumhexafluorophosphate (HBTU), bis(2-oxo-3-oxazolidinyl)phosphonic chloride(BOP-CI), (1H-1,2,3-benzotriazol-1-yloxy)tris(pyrrolidino)phosphoniumhexafluorophosphate (PyBOP), and the like, as well as mixtures thereof.

The coupling agent and the diacid are present in any desired oreffective relative amounts, in one embodiment at least about 1.8 molesof coupling agent per every 1 mole of diacid, in another embodiment atleast about 1.9 moles of coupling agent per every 1 mole of diacid, andin yet another embodiment at least about 2 moles of coupling agent perevery one mole of diacid, and in one embodiment no more than about 2.75moles of coupling agent per every 1 mole of diacid, in anotherembodiment no more than about 2.5 moles of coupling agent per every 1mole of diacid, and in yet another embodiment no more than about 2.2moles of coupling agent per every 1 mole of diacid, although therelative amounts can be outside of these ranges.

Examples of suitable catalysts include 4-dimethylaminopyridine (DMAP),of the formula

triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and the like,as well as mixtures thereof.

The catalyst and the diacid are present in any desired or effectiverelative amounts, in one embodiment at least about 0.05 mole of catalystper every 1 mole of diacid, in another embodiment at least about 0.1mole of catalyst per every 1 mole of diacid, and in yet anotherembodiment at least about 0.2 mole of catalyst per every one mole ofdiacid, and in one embodiment no more than about 1 mole of catalyst perevery 1 mole of diacid, in another embodiment no more than about 0.8mole of catalyst per every 1 mole of diacid, and in yet anotherembodiment no more than about 0.5 mole of catalyst per every 1 mole ofdiacid, although the relative amounts can be outside of these ranges.

Any desired or effective solvent can be employed. Examples of suitablesolvents include methylene chloride, tetrahydrofuran, methyl ethylketone, toluene, dimethyl formamide, diethyl ether, hexane, ethylacetate, and the like, as well as mixtures thereof.

The solvent can be present in any desired or effective amount, in oneembodiment at least about 10 milliliters of solvent per millimole ofdiacid, in another embodiment at least about 15 milliliters of solventper millimole of diacid, and in yet another embodiment at least about 20milliliters of solvent per millimole of diacid, and in one embodiment nomore than about 50 milliliters of solvent per millimole of diacid, inanother embodiment no more than about 40 milliliters of solvent permillimole of diacid, and in yet another embodiment no more than about 30milliliters of solvent per millimole of diacid, although the amount ofsolvent can be outside of these ranges.

The reaction between the diacid, the diamine, and the coupling agent canbe carried out at any desired or effective temperature, in oneembodiment at least about 0° C., in another embodiment at least about 5°C., and in yet another embodiment at least about 15° C., and oneembodiment no more than about 50° C., in another embodiment no more thanabout 40° C., and in yet another embodiment no more than about 30° C.,although the temperature can be outside of these ranges. The subsequentreaction between the resulting amine-terminated diamide intermediate andthe additional diacid can be carried out at any desired or effectivetemperature, in one embodiment at least about 0° C., in anotherembodiment at least about 5° C., and in yet another embodiment at leastabout 15° C., and one embodiment no more than about 50° C., in anotherembodiment no more than about 40° C., and in yet another embodiment nomore than about 30° C., although the temperature can be outside of theseranges. The subsequent reaction between the resulting oligoamideintermediate and the monoalcohol can be carried out at any desired oreffective temperature, in one embodiment at least about 15° C., inanother embodiment at least about 20° C., and in yet another embodimentat least about 25° C., and one embodiment no more than about 40° C., inanother embodiment no more than about 35° C., and in yet anotherembodiment no more than about 30° C., although the temperature can beoutside of these ranges.

When the reaction between the diacid and the diamine takes place as aone-pot process, the reaction can be carried out for any desired oreffective period of time, in one embodiment at least about 2 hours, inanother embodiment at least about 2.5 hours, and in yet anotherembodiment at least about 3 hours, and in one embodiment no more thanabout 5 hours, and in another embodiment no more than about 4 hours,although the period of time can be outside of these ranges.

When the reaction between the diacid, the diamine, and the monoalcoholtakes place in a sequence of steps, the reaction between the diacid, thediamine, and the coupling agent can be carried out for any desired oreffective period of time, in one embodiment at least about 1.5 hours, inanother embodiment at least about 2 hours, and in yet another embodimentat least about 2.5 hours, and in one embodiment no more than about 5hours, in another embodiment no more than about 4 hours, and in anotherembodiment no more than about 3 hours, although the period of time canbe outside of these ranges. The subsequent reaction between theresulting amine-terminated diamide intermediate and the additionaldiacid can be carried out for any desired or effective period of time,in one embodiment at least about 1.5 hours, in another embodiment atleast about 2 hours, and in yet another embodiment at least about 2.5hours, and in one embodiment no more than about 5 hours, in anotherembodiment no more than about 4 hours, and in another embodiment no morethan about 3 hours, although the period of time can be outside of theseranges. The subsequent reaction between the resulting oligoamideintermediate and the monoalcohol can be carried out for any desired oreffective period of time, in one embodiment at least about 1.5 hours, inanother embodiment at least about 2 hours, and in yet another embodimentat least about 2.5 hours, and in one embodiment no more than about 5hours, in another embodiment no more than about 4 hours, and in yetanother embodiment no more than about 3 hours, although the period oftime can be outside of these ranges.

Subsequent to completion of the reaction, the product can be recoveredby any desired or effective method, such as filtration of any solidby-products or washing the solution with water depending on the couplingagent used. The solvent can be removed by rotary evaporation. If needed,the product can be purified by washing with acetone and dried in avacuum oven.

Compounds as disclosed herein can also be prepared by first reactingabout n+1 molar equivalents of a diacid of the formulaHOOC—R₂—COOHand about n molar equivalent of a diamine of the formula

under neat conditions (i.e., in the absence of a solvent) at elevatedtemperatures while removing water from the reaction mixture to form anoligoamide of the formula

Thereafter, the acid-terminated oligoamide thus formed is reacted withabout 2 molar equivalents of a monoalcohol of the formulaR₁—OHby use of a coupling agent such as 1,3-dicyclohexylcarbodiimide (DCC) inthe presence of a catalyst such as 4-dimethylaminopyridine (DMAP) in thepresence of a solvent such as methylene chloride (CH₂Cl₂) at reducedtemperatures. The reaction proceeds as follows:

For example, when n=1, the diacid and the diamine are present in anydesired or effective relative amounts, in one embodiment at least about0.75 mole of diamine per every 2 moles of diacid, in another embodimentat least about 0.85 mole of diamine per every 2 moles of diacid, and inyet another embodiment at least about 1 mole of diamine per every 2moles of diacid, and in one embodiment no more than about 1.5 moles ofdiamine per every 2 moles of diacid, in another embodiment no more thanabout 1.35 moles of diamine per every 2 moles of diacid, and in yetanother embodiment no more than about 1.25 moles of diamine per every 2moles of diacid, although the relative amounts can be outside of theseranges.

Water can be removed from the reaction mixture between the diacid andthe diamine by any desired or effective method, such as by a Dean-Starktrap, molecular sieves or other drying agents, or the like.

The reaction between the diacid and the diamine generally is run neat,i.e., in the absence of a solvent.

The reaction between the diacid and the diamine can be carried out atany desired or effective temperature, in one embodiment at least about130° C., in another embodiment at least about 140° C., and in yetanother embodiment at least about 155° C., and one embodiment no morethan about 180° C., in another embodiment no more than about 175° C.,and in yet another embodiment no more than about 165° C., although thetemperature can be outside of these ranges.

The reaction between the diacid and the diamine can be carried out forany desired or effective period of time, in one embodiment at leastabout 2 hours, in another embodiment at least about 2.5 hours, and inyet another embodiment at least about 3 hours, and in one embodiment nomore than about 5 hours, in another embodiment no more than about 4.5hours, and in another embodiment no more than about 4 hours, althoughthe period of time can be outside of these ranges.

Thereafter, the acid-terminated oligoamide intermediate and themonoalcohol are reacted in the presence of a coupling agent and acatalyst.

Examples of suitable coupling agents include1,3-dicyclohexylcarbodiimide (DCC), of the formula

1-[3-(dimethylamino)propyl] 3-ethylcarbodiimide HCl (EDCI),N,N-carbonyldiimidazole,N-cyclohexyl-N′-(2-morpholinoethyl)-carbodiimidemethyl-p-toluenesulfonate,(benzotriazol-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate(BOP), (obenzotriazol-1-yl)-N,N,N′,N′-bis(tetramethylene)uroniumhexafluorophosphate (HBTU), bis(2-oxo-3-oxazolidinyl)phosphonic chloride(BOP-CI), (1H-1,2,3-benzotriazol-1-yloxy)tris(pyrrolidino)phosphoniumhexafluorophosphate (PyBOP), and the like, as well as mixtures thereof.

Examples of suitable catalysts include 4-dimethylaminopyridine (DMAP),of the formula

triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and the like,as well as mixtures thereof.

The acid-terminated oligoamide intermediate and the monoalcohol arepresent in any desired or effective relative amounts, in one embodimentat least about 2 moles of monoalcohol per every 1 mole ofacid-terminated oligoamide intermediate, in another embodiment at leastabout 2.15 moles of monoalcohol per every 1 mole of acid-terminatedoligoamide intermediate, and in yet another embodiment at least about2.25 moles of monoalcohol per every one mole of acid-terminatedoligoamide intermediate, and in one embodiment no more than about 2.75moles of monoalcohol per every 1 mole of acid-terminated oligoamideintermediate, in another embodiment no more than about 2.5 moles ofmonoalcohol per every 1 mole of acid-terminated oligoamide intermediate,and in yet another embodiment no more than about 2.4 moles ofmonoalcohol per every 1 mole of acid-terminated oligoamide intermediate,although the relative amounts can be outside of these ranges.

The acid-terminated oligoamide and the coupling agent are present in anydesired or effective relative amounts, in one embodiment at least about1.8 moles of coupling agent per every 1 mole of acid-terminatedoligoamide, in another embodiment at least about 2 moles of couplingagent per every 1 mole of acid-terminated oligoamide, and in yet anotherembodiment at least about 2.2 moles of coupling agent per every one moleof acid-terminated oligoamide, and in one embodiment no more than about3 moles of coupling agent per every 1 mole of acid-terminatedoligoamide, in another embodiment no more than about 2.8 moles ofcoupling agent per every 1 mole of acid-terminated oligoamide, and inyet another embodiment no more than about 2.5 moles of coupling agentper every 1 mole of acid-terminated oligoamide, although the relativeamounts can be outside of these ranges.

The catalyst and the acid-terminated oligoamide intermediate are presentin any desired or effective relative amounts, in one embodiment at leastabout 0.05 mole of catalyst per every 1 mole of acid-terminatedoligoamide intermediate, in another embodiment at least about 0.1 moleof catalyst per every 1 mole of acid-terminated oligoamide intermediate,and in yet another embodiment at least about 0.2 mole of catalyst perevery one mole of acid-terminated oligoamide intermediate, and in oneembodiment no more than about 1 mole of catalyst per every 1 mole ofacid-terminated oligoamide intermediate, in another embodiment no morethan about 0.8 mole of catalyst per every 1 mole of acid-terminatedoligoamide intermediate, and in yet another embodiment no more thanabout 0.5 mole of catalyst per every 1 mole of acid-terminatedoligoamide intermediate, although the relative amounts can be outside ofthese ranges.

Any desired or effective solvent can be employed. Examples of suitablesolvents include methylene chloride, tetrahydrofuran, methyl ethylketone, toluene, dimethyl formamide, diethyl ether, hexane, ethylacetate, and the like, as well as mixtures thereof.

The solvent can be present in any desired or effective amount, in oneembodiment at least about 20 milliliters of solvent per gram ofacid-terminated oligoamide intermediate, in another embodiment at leastabout 25 milliliters of solvent per gram of acid-terminated oligoamideintermediate, and in yet another embodiment at least about 30milliliters of solvent per gram of acid-terminated oligoamideintermediate, and in one embodiment no more than about 100 millilitersof solvent per gram of acid-terminated oligoamide intermediate, inanother embodiment no more than about 90 milliliters of solvent per gramof acid-terminated oligoamide intermediate, and in yet anotherembodiment no more than about 80 milliliters of solvent per gram ofacid-terminated oligoamide intermediate, although the amount of solventcan be outside of these ranges.

The reaction between the acid-terminated oligoamide intermediate, themonoalcohol, and the coupling agent can be carried out at any desired oreffective temperature, in one embodiment at least about 15° C., inanother embodiment at least about 20° C., and in yet another embodimentat least about 25° C., and one embodiment no more than about 50° C., inanother embodiment no more than about 40° C., and in yet anotherembodiment no more than about 35° C., although the temperature can beoutside of these ranges.

The reaction between the acid-terminated oligoamide intermediate, themonoalcohol, and the coupling agent can be carried out for any desiredor effective period of time, in one embodiment at least about 2 hours,in another embodiment at least about 2.5 hours, and in yet anotherembodiment at least about 3 hours, and in one embodiment no more thanabout 5 hours, in another embodiment no more than about 4.5 hours, andin another embodiment no more than about 4 hours, although the period oftime can be outside of these ranges.

Subsequent to completion of the reaction, the product can be recoveredby any desired or effective method, such as filtration of any solidby-products or washing the solution with water depending on the couplingagent used. The solvent can be removed by rotary evaporation. If needed,the product can be purified by washing with acetone and dried in avacuum oven.

Many embodiments of the compounds thus prepared can exhibit gel-likebehavior when present in solutions. Examples of materials in which theycan be dissolved include curable monomers such as, for example,propoxylated neopentyl glycol diacrylate, such as SR9003, commerciallyavailable from Sartomer Co. Inc. By gel-like behavior is meant that theyundergo a relatively sharp increase in viscosity over a relativelynarrow temperature range. In one embodiment, some compounds as disclosedherein undergo a change in viscosity of at least about 10³ centipoise,in another embodiment at least about 10⁵ centipoise, and in yet anotherembodiment at least about 10⁶ centipoise over a temperature range of inone embodiment at least about 5° C., in another embodiment at leastabout 10° C., and in yet another embodiment at least about 30° C.,although the viscosity change and temperature range can be outside ofthese ranges, and compounds that do not undergo changes within theseranges are also included herein.

At least some embodiments of the compounds disclosed herein can form asemi-solid gel at a first temperature. For example, when the compound isincorporated into a phase change ink, this temperature is below thespecific temperature at which the ink is jetted. The semi-solid gelphase is a physical gel that exists as a dynamic equilibrium comprisingone or more solid gellant molecules and a liquid solvent. The semi-solidgel phase is a dynamic networked assembly of molecular components heldtogether by non-covalent interactions such as hydrogen bonding, Van derWaals interactions, aromatic non-bonding interactions, ionic orcoordination bonding, London dispersion forces, or the like, which, uponstimulation by physical forces, such as temperature, mechanicalagitation, or the like, or chemical forces, such as pH, ionic strength,or the like, can undergo reversible transitions from liquid tosemi-solid state at the macroscopic level. The solutions containing thegellant molecules exhibit a thermally reversible transition between thesemi-solid gel state and the liquid state when the temperature is variedabove or below the gel point of the solution. This reversible cycle oftransitioning between semi-solid gel phase and liquid phase can berepeated many times in the solution formulation.

The compounds disclosed herein are curable. “Curable” as used hereinmeans polymerizable or chain extendable, i.e., a material that can becured via polymerization, including (but not limited to) free radicalpolymerization or chain extension, cationic polymerization or chainextension, and/or in which polymerization is photoinitiated through useof a radiation sensitive photoinitiator. Radiation curable as usedherein is intended to cover all forms of curing upon exposure to aradiation source, including (but not limited to) light and heat sourcesand including in the presence or absence of initiators. Examples ofradiation curing include (but are not limited to) ultraviolet (UV)light, for example having a wavelength of from about 200 to about 400nanometers, visible light, or the like, optionally in the presence ofphotoinitiators and/or sensitizers, e-beam radiation, optionally in thepresence of photoinitiators, thermal curing, optionally in the presenceof high temperature thermal initiators (and which are preferably largelyinactive at the jetting temperature when used in phase change inks), andappropriate combinations thereof.

Also disclosed herein is a phase change ink comprising a colorant, aninitiator, and a phase change ink carrier, said carrier comprising acompound of the formula

wherein R₁ and R₁′ each, independently of the other, is (i) an alkylgroup having at least one ethylenic unsaturation therein (includinglinear and branched, cyclic and acyclic, and substituted andunsubstituted alkyl groups, and wherein hetero atoms either may or maynot be present in the alkyl group), (ii) an arylalkyl group having atleast one ethylenic unsaturation therein (including substituted andunsubstituted arylalkyl groups, wherein the alkyl portion of thearylalkyl group can be linear or branched, cyclic or acyclic, andsubstituted or unsubstituted, and wherein hetero atoms either may or maynot be present in either the aryl or the alkyl portion of the arylalkylgroup), or (iii) an alkylaryl group having at least one ethylenicunsaturation therein (including substituted and unsubstituted alkylarylgroups, wherein the alkyl portion of the alkylaryl group can be linearor branched, cyclic or acyclic, and substituted or unsubstituted, andwherein hetero atoms either may or may not be present in either the arylor the alkyl portion of the alkylaryl group), R₂, R₂′, and R₃ each,independently of the others, are (i) alkylene groups, including linearand branched, saturated and unsaturated, cyclic and acyclic, andsubstituted and unsubstituted alkylene groups, and wherein hetero atomseither may or may not be present in the alkylene group, (ii) arylenegroups, including substituted and unsubstituted arylene groups, andwherein hetero atoms either may or may not be present in the arylenegroup, (iii) arylalkylene groups, including substituted andunsubstituted arylalkylene groups, wherein the alkyl portion of thearylalkylene group can be linear or branched, saturated or unsaturated,cyclic or acyclic, and substituted or unsubstituted, and wherein heteroatoms either may or may not be present in either the aryl or the alkylportion of the arylalkylene group, or (iv) alkylarylene groups,including substituted and unsubstituted alkylarylene groups, wherein thealkyl portion of the alkylarylene group can be linear or branched,saturated or unsaturated, cyclic or acyclic, and substituted orunsubstituted, and wherein hetero atoms either may or may not be presentin either the aryl or the alkyl portion of the alkylarylene group, and nis an integer representing the number of repeat amide units and is atleast 1.

The compound of the formula

is present in the phase change ink in any desired or effective amount,in one embodiment at least about 5 percent by weight of the ink carrier,in another embodiment at least about 7.5 percent by weight of the inkcarrier, and in yet another embodiment at least about 10 percent byweight of the ink carrier, and in one embodiment no more than about 50percent by weight of the ink carrier, in another embodiment no more thanabout 40 percent by weight of the ink carrier, and in yet anotherembodiment no more than about 30 percent by weight of the ink carrier,although the amount can be outside of these ranges.

The compounds disclosed herein can, in at least some embodiments, act asan organic gellant in the ink to the viscosity of the ink within adesired temperature range. In particular, the gellant can in someembodiments form a semi-solid gel in the ink vehicle at temperaturesbelow the specific temperature at which the ink is jetted.

The ink vehicle further contains at least one radically curable monomercompound. Examples of suitable monomer compounds include (but are notlimited to) propoxylated neopentyl diacrylate, such as SR9003,commercially available from Sartomer Co. Inc., isobornyl acrylate,isobornyl methacrylate, lauryl acrylate, lauryl methacrylate,isodecylacrylate, isodecylmethacrylate, caprolactone acrylate,2-phenoxyethyl acrylate, isooctylacrylate, isooctylmethacrylate, butylacrylate, and the like, as well as mixtures thereof. In addition,multifunctional acrylate and methacrylate monomers and oligomers can beincluded in the phase change ink carrier as reactive diluents and asmaterials that can increase the crosslink density of the cured image,thereby enhancing the toughness of the cured images. Examples ofsuitable multifunctional acrylate and methacrylate monomers andoligomers include (but are not limited to) pentaerythritoltetraacrylate, pentaerythritol tetramethacrylate, 1,2-ethylene glycoldiacrylate, 1,2-ethylene glycol dimethacrylate, 1,6-hexanedioldiacrylate, 1,6-hexanediol dimethacrylate, 1,12-dodecanol diacrylate,1,12-dodecanol dimethacrylate, tris(2-hydroxy ethyl)isocyanuratetriacrylate, hexanediol diacrylate, tripropylene glycol diacrylate,dipropylene glycol diacrylate, amine modified polyether acrylates(available as PO 83 F, LR 8869, and/or LR 8889 (all available from BASFCorporation), trimethylolpropane triacrylate, glycerol propoxylatetriacrylate, dipentaerythritol pentaacrylate, dipentaerythritolhexaacrylate, ethoxylated pentaerythritol tetraacrylate (available fromSartomer Co. Inc. as SR 494), and the like, as well as mixtures thereof.When a reactive diluent is added to the ink carrier material, thereactive diluent is added in any desired or effective amount, in oneembodiment at least about 1 percent by weight of the carrier, and inanother embodiment at least about 35 percent by weight of the carrier,and in one embodiment no more than about 80 percent by weight of thecarrier, and in another embodiment no more than about 70 percent byweight of the carrier, although the amount of diluent can be outside ofthese ranges.

The ink carrier is present in the phase change ink in any desired oreffective amount, in one embodiment of at least about 0.1 percent byweight of the ink, in another embodiment of at least about 50 percent byweight of the ink, in yet another embodiment of at least about 70percent by weight of the ink, and in still another embodiment of atleast about 90 percent by weight of the ink, and in one embodiment of nomore than about 97 percent by weight of the ink, in another embodimentof no more than about 95 percent by weight of the ink, and in yetanother embodiment of no more than about 85 percent by weight of theink, although the amount can be outside of these ranges.

The ink compositions further contain an initiator.

Examples of free radical initiators include benzyl ketones, monomerichydroxyl ketones, polymeric hydroxyl ketones, α-amino ketones, acylphosphine oxides, metallocenes, benzophenone, benzophenone derivatives,and the like. Specific examples include1-hydroxy-cyclohexylphenylketone, benzophenone,2-benzyl-2-(dimethylamino)-1-(4-(4-morphorlinyl)phenyl)-1-butanone,2-methyl-1-(4-methylthio)phenyl-2-(4-morphorlinyl)-1-propanone,diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, benzyl-dimethylketal,isopropylthioxanthone, and the like, as well as mixtures thereof.Specific examples include 1-hydroxy-cyclohexylphenylketone,benzophenone,2-benzyl-2-(dimethylamino)-1-(4-(4-morphorlinyl)phenyl)-1-butanone,2-methyl-1-(4-methylthio)phenyl-2-(4-morphorlinyl)-1-propanone,diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, benzyl-dimethylketal,isopropylthioxanthone, 2,4,6-trimethylbenzoyidiphenylphosphine oxide(available as BASF LUCIRIN TPO),2,4,6-trimethylbenzoylethoxyphenylphosphine oxide (available as BASFLUCIRIN TPO-L), bis(2,4,6-trimethylbenzoyl)-phenyl-phosphine oxide(available as Ciba IRGACURE 819) and other acyl phosphines,2-methyl-1-(4-methylthio)phenyl-2-(4-morphorlinyl)-1-propanone(available as Ciba IRGACURE 907) and1-(4-(2-hydroxyethoxy)phenyl)-2-hydroxy-2-methylpropan-1-one (availableas Ciba IRGACURE 2959), 2-benzyl 2-dimethylamino1-(4-morpholinophenyl)butanone-1 (available as Ciba IRGACURE 369),2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)-benzyl)-phenyl)-2-methylpropan-1-one(available as Ciba IRGACURE 127),2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butanone(available as Ciba IRGACURE 379), titanocenes, isopropylthioxanthone,1-hydroxy-cyclohexylphenylketone, benzophenone,2,4,6-trimethylbenzophenone, 4-methylbenzophenone,diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide,2,4,6-trimethylbenzoylphenylphosphinic acid ethyl ester,oligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)propanone),2-hydroxy-2-methyl-1-phenyl-1-propanone, benzyl-dimethylketal, and thelike, as well as mixtures thereof.

Optionally, the phase change inks can also contain an amine synergist,which are co-initiators which can donate a hydrogen atom to aphotoinitiator and thereby form a radical species that initiatespolymerization, and can also consume dissolved oxygen, which inhibitsfree-radical polymerization, thereby increasing the speed ofpolymerization. Examples of suitable amine synergists include (but arenot limited to) ethyl-4-dimethylaminobenzoate,2-ethylhexyl-4-dimethylaminobenzoate, and the like, as well as mixturesthereof.

Initiators for inks disclosed herein can absorb radiation at any desiredor effective wavelength, in one embodiment at least about 200nanometers, and in one embodiment no more than about 560 nanometers, andin another embodiment no more than about 420 nanometers, although thewavelength can be outside of these ranges.

The initiator can be present in the ink in any desired or effectiveamount, in one embodiment at least about 0.5 percent by weight of theink, and in another embodiment at least about 1 percent by weight of theink, and in one embodiment no more than about 15 percent by weight ofthe ink, and in another embodiment no more than about 10 percent byweight of the ink, although the amount can be outside of these ranges.

The radiation curable phase change inks can also optionally contain anantioxidant. The optional antioxidants can protect the images fromoxidation and can also protect the ink components from oxidation duringthe heating portion of the ink preparation process. Specific examples ofsuitable antioxidant stabilizers include (but are not limited to)NAUGARD® 524, NAUGARD® 635, NAUGARD® A, NAUGARD® 1-403, and NAUGARD®959, commercially available from Crompton Corporation, Middlebury,Conn.; IRGANOX® 1010 and IRGASTAB® UV 10, commercially available fromCiba Specialty Chemicals; GENORAD 16 and GENORAD 40 commerciallyavailable from Rahn AG, Zurich, Switzerland, and the like, as well asmixtures thereof. When present, the optional antioxidant is present inthe ink in any desired or effective amount, in one embodiment at leastabout 0.01 percent by weight of the ink carrier, in another embodimentat least about 0.1 percent by weight of the ink carrier, and in yetanother embodiment at least about 1 percent by weight of the inkcarrier, and in one embodiment no more than about 20 percent by weightof the ink carrier, in another embodiment no more than about 5 percentby weight of the ink carrier, and in yet another embodiment no more thanabout 3 percent by weight of the ink carrier, although the amount can beoutside of these ranges.

The phase change inks also contain a colorant. Any desired or effectivecolorant can be employed, including dyes, pigments, mixtures thereof,and the like, provided that the colorant can be dissolved or dispersedin the ink vehicle. Examples of suitable dyes include, but are notlimited to, Usharect Blue 86 (Direct Blue 86), available from UshantiColour; Intralite Turquoise 8GL (Direct Blue 86), available from ClassicDyestuffs; Chemictive Brilliant Red 7BH (Reactive Red 4), available fromChemiequip; Levafix Black EB, available from Bayer; Reactron Red H₈B(Reactive Red 31), available from Atlas Dye-Chem; D&C Red #28 (Acid Red92), available from Warner-Jenkinson; Direct Brilliant Pink B, availablefrom Global Colors; Acid Tartrazine, available from MetrochemIndustries; Cartasol Yellow 6GF, available from Clariant; Carta Blue2GL, available from Clariant; solvent dyes, including spirit solubledyes such as Neozapon Red 492 (BASF); Orasol Red G (Ciba); DirectBrilliant Pink B (Global Colors); Aizen Spilon Red C-BH (HodogayaChemical); Kayanol Red 3BL (Nippon Kayaku); Spirit Fast Yellow 3G; AizenSpilon Yellow C-GNH (Hodogaya Chemical); Cartasol Brilliant Yellow 4GF(Clariant); Pergasol Yellow CGP (Ciba); Orasol Black RLP (Ciba); SavinylBlack RLS (Clariant); Morfast Black Conc. A (Rohm and Haas); Orasol BlueGN (Ciba); Savinyl Blue GLS (Sandoz); Luxol Fast Blue MBSN (Pylam);Sevron Blue 5GMF (Classic Dyestuffs); Basacid Blue 750 (BASF); NeozaponBlack X51 [C.I. Solvent Black, C.I. 12195] (BASF); Sudan Blue 670 [C.I.61554] (BASF); Sudan Yellow 146 [C.I. 12700] (BASF); Sudan Red 462 [C.I.260501] (BASF); and the like, as well as mixtures thereof.

Pigments are also suitable colorants for the phase change inks. Examplesof suitable pigments include PALIOGEN Violet 5100 (BASF); PALIOGENViolet 5890 (BASF); HELIOGEN Green L8730 (BASF); LITHOL Scarlet D3700(BASF); SUNFAST® Blue 15:4 (Sun Chemical); Hostaperm Blue B2G-D(Clariant); Permanent Red P-F7RK; Hostaperm Violet BL (Clariant); LITHOLScarlet 4440 (BASF); Bon Red C (Dominion Color Company); ORACET Pink RF(Ciba); PALIOGEN Red 3871 K (BASF); SUNFAST® Blue 15:3 (Sun Chemical);PALIOGEN Red 3340 (BASF); SUNFAST® Carbazole Violet 23 (Sun Chemical);LITHOL Fast Scarlet L4300 (BASF); SUNBRITE Yellow 17 (Sun Chemical);HELIOGEN Blue L6900, L7020 (BASF); SUNBRITE Yellow 74 (Sun Chemical);SPECTRA PAC® C Orange 16 (Sun Chemical); HELIOGEN Blue K6902, K6910(BASF); SUNFAST® Magenta 122 (Sun Chemical); HELIOGEN Blue D6840, D7080(BASF); Sudan Blue OS (BASF); NEOPEN Blue FF4012 (BASF); PV Fast BlueB2GO1 (Clariant); IRGALITE Blue BCA (Ciba); PALIOGEN Blue 6470 (BASF);Sudan Orange G (Aldrich), Sudan Orange 220 (BASF); PALIOGEN Orange 3040(BASF); PALIOGEN Yellow 152, 1560 (BASF); LITHOL Fast Yellow 0991 K(BASF); PALIOTOL Yellow 1840 (BASF); NOVOPERM Yellow FGL (Clariant);Lumogen Yellow D0790 (BASF); Suco-Yellow L1250 (BASF); Suco-Yellow D1355(BASF); Suco Fast Yellow D1355, D1351 (BASF); HOSTAPERM Pink E 02(Clariant); Hansa Brilliant Yellow 5GX03 (Clariant); Permanent YellowGRL 02 (Clariant); Permanent Rubine L6B 05 (Clariant); FANAL Pink D4830(BASF); CINQUASIA Magenta (DU PONT); PALIOGEN Black L0084 (BASF);Pigment Black K801 (BASF); and carbon blacks such as REGAL 330™ (Cabot),Carbon Black 5250, Carbon Black 5750 (Columbia Chemical), and the like,as well as mixtures thereof.

In another specific embodiment, the colorant is a curable olefincolorant such as those disclosed in U.S. Pat. No. 6,870,063, U.S. Pat.No. 6,870,062, U.S. Pat. No. 6,787,658, and U.S. patent Publication20040142995, the disclosures of each of which are totally incorporatedherein by reference.

The colorant is present in the phase change ink in any desired oreffective amount to obtain the desired color or hue, in one embodimentat least about 0.1 percent by weight of the ink, and in anotherembodiment at least about 0.2 percent by weight of the ink, and in oneembodiment no more than about 15 percent by weight of the ink, and inanother embodiment no more than about 8 percent by weight of the ink,although the amount can be outside of these ranges.

The radiation curable phase change inks can also, if desired, containadditives to take advantage of the known functionality associated withsuch additives. Such additives may include, for example, defoamers, slipand levelling agents, pigment dispersants, and the like, as well asmixtures thereof. The inks can also include additional monomeric orpolymeric materials as desired.

Curing of the ink can be effected by exposure of the ink image toactinic radiation at any desired or effective wavelength, in oneembodiment at least about 200 nanometers, and one embodiment no morethan about 480 nanometers, although the wavelength can be outside ofthese ranges. Exposure to actinic radiation can be for any desired oreffective period of time, in one embodiment for at least about 0.2second, in another embodiment for at least about 1 second, and in yetanother embodiment for at least about 5 seconds, and in one embodimentfor no more than about 30 seconds, and in another embodiment for no morethan about 15 seconds, although the exposure period can be outside ofthese ranges. By curing is meant that the curable compounds in the inkundergo an increase in molecular weight upon exposure to actinicradiation, such as (but not limited to) crosslinking, chain lengthening,or the like.

The ink compositions generally have melt viscosities at the jettingtemperature (in one embodiment no lower than about 50° C., in anotherembodiment no lower than about 60° C., and in yet another embodiment nolower than about 70° C., and in one embodiment no higher than about 120°C., and in another embodiment no higher than about 110° C., although thejetting temperature can be outside of these ranges) in one embodiment ofno more than about 30 centipoise, in another embodiment of no more thanabout 20 centipoise, and in yet another embodiment of no more than about15 centipoise, and in one embodiment of no less than about 2 centipoise,in another embodiment of no less than about 5 centipoise, and in yetanother embodiment of no less than about 7 centipoise, although the meltviscosity can be outside of these ranges.

In one specific embodiment, the inks are jetted at low temperatures, inparticular at temperatures below about 110° C., in one embodiment fromabout 40° C. to about 110° C., in another embodiment from about 50° C.to about 110° C., and in yet another embodiment from about 60° C. toabout 90° C., although the jetting temperature can be outside of theseranges. At such low jetting temperatures, the conventional use oftemperature differential between the jetted ink and the substrate uponwhich the ink is jetted to effect a rapid phase change in the ink (i.e.,from liquid to solid) may not be effective. The gellant can thus be usedto effect a rapid viscosity increase in the jetted ink upon thesubstrate. In particular, jetted ink droplets can be pinned intoposition on a receiving substrate such as a final recording substrate,such as paper or transparency material, or an intermediate transfermember, such as a transfuse drum or belt, that is maintained at atemperature cooler than the ink jetting temperature of the ink throughthe action of a phase change transition in which the ink undergoes asignificant viscosity change from a liquid state to a gel state (orsemi-solid state).

In some embodiments, the temperature at which the ink forms the gelstate is any temperature below the jetting temperature of the ink, inone embodiment any temperature that is about 5° C. or more below thejetting temperature of the ink. In one embodiment, the gel state can beformed at a temperature of at least about 25° C., and in anotherembodiment at a temperature of at least about 30° C., and in oneembodiment of no more than about 100° C., in another embodiment of nomore than about 70° C., and in yet another embodiment of no more thanabout 50° C., although the temperature can be outside of these ranges. Arapid and large increase in ink viscosity occurs upon cooling from thejetting temperature, at which the ink is in a liquid state, to the geltemperature, at which the ink is in the gel state. The viscosityincrease is in one specific embodiment at least a 10^(2.5)-fold increasein viscosity.

It has been found that optimum transfer efficiency from an intermediatetransfer surface to a final recording sheet and optimum print qualitycan be achieved if the viscosity of the ink image deposited on theintermediate transfer member is greatly increased after jetting the ink,so as to obtain a stable and transferable image that will not smear. Asuitable gelling agent for the ink will gel the monomers/oligomers inthe ink vehicle quickly and reversibly and will demonstrate a narrowphase change transition, for example within a temperature range of fromabout 30° C. to about 100° C., preferably of from about 30° C. to about70° C., although the transition range can be outside of thesetemperature ranges. The gel state of the ink in one specific embodimentexhibits a minimum of 10^(2.5) centipoise, and in another specificembodiment 10³ centipoise, increase in viscosity at transferringtemperatures, e.g., in one specific embodiment from about 30 to about70° C., compared to the viscosity at the jetting temperature. Onespecific embodiment is directed to gellant containing inks that rapidlyincrease in viscosity within from about 5° C. to about 10° C. below thejetting temperature and ultimately reach a viscosity above 10⁴ times thejetting viscosity, and in another embodiment about 10⁵ times the jettingviscosity, although the viscosity can be outside of these ranges.

When the inks are in the gel state, the viscosity of the ink is in oneembodiment at least about 1,000 centipoise, in another embodiment atleast about 10,000 centipoise, and in yet another embodiment at leastabout 100,000 centipoise, although the viscosity can be outside of theseranges. Viscosity values in the gel state are in one embodiment at leastabout 10³ centipoise, and in another embodiment at least about 10^(4.5)centipoise, and in one embodiment no more than about 10⁹ centipoise, andin another embodiment no more than about 10^(6.5) centipoise, althoughthe gel state viscosity can be outside of these ranges. The preferredgel phase viscosity can vary with the print process. For example, thehighest viscosities are preferred when employing intermediate transfer,or when jetting directly to porous paper in order to minimize theeffects of ink bleed and feathering. On the other hand, less poroussubstrates such as plastic may lead to the use of lower ink viscositiesthat control dot gain and agglomeration of individual ink pixels. Thegel viscosity can be controlled by ink formulation and substratetemperature. An additional benefit of the gel state for radiationcurable inks is that higher viscosities of about 10³ to about 10⁴centipoise can reduce oxygen diffusion in the ink, which in turn canlead to a faster rate of cure in free radical initiation.

For printing applications wherein the ink is printed onto anintermediate transfer member and subsequently transferred to a finalsubstrate, the viscosity of the ink in one specific embodiment increasesto about 10⁶ centipoise or greater at the intermediate transfer membertemperature to facilitate adhesion to the intermediate transfer member,and for printing applications wherein the ink is printed directly onto afinal substrate, the viscosity of the ink in one specific embodimentincreases to 106 centipoise or greater at the final substratetemperature to prevent the ink from soaking into the final substrateand/or to facilitate adhesion to the final substrate until curing byexposure to radiation. In one specific embodiment, the temperature ofthe intermediate transfer member or the final substrate onto which theink is printed and at which the ink viscosity increases to about 10⁶centipoise or greater is about 50° C. or lower.

The ink compositions can be prepared by any desired or suitable method.For example, the ink ingredients can be mixed together, followed byheating, to a temperature in one embodiment of at least about 80° C.,and in one embodiment of no more than about 120° C., although thetemperature can be outside of these ranges, and stirring until ahomogeneous ink composition is obtained, followed by cooling the ink toambient temperature (typically from about 20 to about 25° C.). The inksare solid at ambient temperature.

The inks can be employed in apparatus for direct printing ink jetprocesses and in indirect (offset) printing ink jet applications.Another embodiment disclosed herein is directed to a process whichcomprises incorporating an ink as disclosed herein into an ink jetprinting apparatus, melting the ink, and causing droplets of the meltedink to be ejected in an imagewise pattern onto a recording substrate. Adirect printing process is also disclosed in, for example, U.S. Pat. No.5,195,430, the disclosure of which is totally incorporated herein byreference. Yet another embodiment disclosed herein is directed to aprocess which comprises incorporating an ink as disclosed herein into anink jet printing apparatus, melting the ink, causing droplets of themelted ink to be ejected in an imagewise pattern onto an intermediatetransfer member, and transferring the ink in the imagewise pattern fromthe intermediate transfer member to a final recording substrate. In aspecific embodiment, the intermediate transfer member is heated to atemperature above that of the final recording sheet and below that ofthe melted ink in the printing apparatus. An offset or indirect printingprocess is also disclosed in, for example, U.S. Pat. No. 5,389,958, thedisclosure of which is totally incorporated herein by reference. In onespecific embodiment, the printing apparatus employs a piezoelectricprinting process wherein droplets of the ink are caused to be ejected inimagewise pattern by oscillations of piezoelectric vibrating elements.Inks as disclosed herein can also be employed in other hot melt printingprocesses, such as hot melt acoustic ink jet printing, hot melt thermalink jet printing, hot melt continuous stream or deflection ink jetprinting, and the like. Phase change inks as disclosed herein can alsobe used in printing processes other than hot melt ink jet printingprocesses.

Any suitable substrate or recording sheet can be employed, includingplain papers such as XEROX® 4024 papers, XEROX® Image Series papers,Courtland 4024 DP paper, ruled notebook paper, bond paper, silica coatedpapers such as Sharp Company silica coated paper, JuJo paper, HAMMERMILLLASERPRINT® paper, and the like, glossy coated papers such as XEROX®Digital Color Gloss, Sappi Warren Papers LUSTROGLOSS®, and the like,transparency materials, fabrics, textile products, plastics, polymericfilms, inorganic substrates such as metals and wood, and the like.

Specific embodiments will now be described in detail. These examples areintended to be illustrative, and the claims are not limited to thematerials, conditions, or process parameters set forth in theseembodiments. All parts and percentages are by weight unless otherwiseindicated.

EXAMPLE I

A compound of the formula

wherein —C₃₄H_(56+a)— represents a branched alkylene group which mayinclude unsaturations and cyclic groups, wherein a is an integer of 0,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 and n is 1, including (but notlimited to) isomers of the formula

wherein n is 1 was prepared as follows. EMPOL® 1008 C36 dimer diacid (2eq, 20 mmoles, 11.56 g; obtained from Cognis Canada Ltd., Mississauga,Ontario) was dissolved in 200 mL dichloromethane in a round bottom flaskunder inert atmosphere. The solution was cooled to 0° C. and4-dimethylaminopyridine (DMAP) (0.4 eq, 4 mmoles, 0.48 g; obtained fromSigma-Aldrich Fine Chemicals, Milwaukee, Wis.) was added. After the DMAPwas completely dissolved, a 1 M solution of 1,3-dicyclohexylcarbodiimide(DCC) in dichloromethane (4 eq, 40 mmoles, 40 mL; obtained fromSigma-Aldrich Fine Chemicals) was added, and the solution was stirredfor 20 minutes. Ethylene diamine (1 eq, 10 mmoles, 0.6 g; obtained fromSigma-Aldrich Fine Chemicals) was then added, and the solution wasbrought to room temperature and stirred for 2 hours. Ethoxylated (2)hydroxyethyl methacrylate (CD570, 2 eq, 20 mmoles, 4.365 g; obtainedfrom Sartomer Company Inc. Exton, Pa.) was added and the solution wasstirred for an additional 2 hours. The reaction mixture was subsequentlyfiltered to remove N,N′-dicyclohexylurea byproduct (DCHU). The solventswere removed from the filtrate by rotary evaporation. The crude productwas then washed with acetone, filtered, and dried in a vacuum oven. Theamide gellant product was obtained as a white semi-solid in 68.2% yield(10.6 g). Elemental analysis calculated for C, 74.43%; H, 10.9%; N,2.63%. Found for C, 74.42%; H, 11.95%; N, 2.63%.

EXAMPLE II

A compound of the formula

wherein —C₃₄H_(56+a)— represents a branched alkylene group which mayinclude unsaturations and cyclic groups, wherein a is an integer of 0,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, including (but not limited to)isomers of the formula

wherein n is 2 was prepared as follows. EMPOL® 1008 C36 dimer diacid (1eq, 10 mmoles, 5.68 g) was dissolved in dichloromethane (200 mL) in a500 mL round bottomed flask under inert atmosphere. The solution wascooled to 0° C. and 4-dimethylaminopyridine (DMAP, 0.2 eq, 2 mmoles,0.24 g) was added. After the DMAP had dissolved, a solution of1,3-dicyclohexylcarbodiimide (DCC, 1 M in dichloromethane, 2 eq, 20mmols, 20 mL) was added. After the solution was stirred for 20 minutes,ethylene diamine (2 eq, 20 mmoles, 1.2 g) was added and stirred for twohours at room temperature to give the following complex (hereinafterreferred to as solution (I)):

wherein —C₃₄H_(56+a)— represents a branched alkylene group which mayinclude unsaturations and cyclic groups, wherein a is an integer of 0,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 and n is 2, including (but notlimited to) isomers of the formula

In a 1000 mL round bottom flask, EMPOL® 1008 C36 dimer diacid (2 eq, 20mmoles, 11.36 g) was dissolved in 200 mL dichloromethane under inertatmosphere. The solution was cooled to 0° C. and DMAP (0.4 eq, 4 mmoles,0.48 g) was added, followed by a 1 M solution of DCC in dichloromethane(4 eq, 40 mmoles, 40 mL). After 20 minutes, solution (I) was added andthe reaction mixture was brought to room temperature. The mixture wasstirred for 2 hours under inert atmosphere. Thereafter, ethoxylatedhydroxyethyl methacrylate (CD570, 2 eq, 20 mmoles, 4.365 g) was addedand the solution was stirred for an additional 2 hours. The reactionmixture was then filtered to remove N,N′-dicyclohexylurea byproduct(DCHU). The solvents were subsequently removed from the filtrate byrotary evaporation. The crude product was then washed with acetone,filtered, and dried in a vacuum oven. The amide gellant was obtained asa white semi-solid in 70.5% yield (15.2 g). Elemental analysiscalculated for C, 72.49%; H, 11.31%; N, 1.79%. Found for C, 70.64%; H,11.49%; N, 2.88%.

EXAMPLE III

The process of Example I was repeated except that the ethoxylatedhydroxyethyl methacrylate (CD570) was replaced with caprolactoneacrylate (available as TONE® M-100 from Dow Chemical, Midland, Mich.).The resulting product was obtained as a white waxy solid in 72% yield(63 g) and was believed to be of the formula

wherein —C₃₄H_(56+a)— represents a branched alkylene group which mayinclude unsaturations and cyclic groups, wherein a is an integer of 0,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 and n is 1, including (but notlimited to) isomers of the formula

wherein n=1. ¹H NMR (CDCl₃, 300 MHz, at room temperature): 50.89-1.80(220H, m), 2.29-2.39 (12H, m), 2.55 (2H, br. s), 3.38 (4H, s), 4.07 (8H,t, J=6.6 Hz), 4.37 (8H, m), 5.90 (2H, dd, J=10.4, 1.4 Hz), 6.16 (2H, dd,J=17.3, 10.4 Hz), 6.42 (2H, d, J=17.3, 1.4 Hz).

EXAMPLE IV

The process of Example I was repeated except that the ethoxylatedhydroxyethyl methacrylate (CD570) was replaced with ethoxylated (5)hydroxyethyl methacrylate (CD571), obtained from Sartomer Company Inc.Exton, Pa. The resulting product was obtained as a yellowish semi-solidin 92.5% yield (15.12 g) and was believed to be of the formula

wherein —C₃₄H_(56+a)— represents a branched alkylene group which mayinclude unsaturations and cyclic groups, wherein a is an integer of 0,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 and n is 1, including (but notlimited to) isomers of the formula

wherein n=1.

EXAMPLE V

The process of Example I was repeated except that the ethoxylatedhydroxyethyl methacrylate (CD570) was replaced with 2-hydroxyethylacrylate, available from Sigma-Aldrich Fine Chemicals. The resultingproduct was obtained as a white semi-solid in 84.9% yield (11 g) and wasbelieved to be of the formula

wherein —C₃₄H_(56+a)— represents a branched alkylene group which mayinclude unsaturations and cyclic groups, wherein a is an integer of 0,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 and n is 1, including (but notlimited to) isomers of the formula

wherein n is 1.

EXAMPLE VI

The process of Example I was repeated except that the ethoxylatedhydroxyethyl methacrylate (CD570) was replaced with 1,4-butanediol vinylether, available from Sigma-Aldrich Fine Chemicals, Milwaukee, Wis. Theresulting product was obtained as a yellowish semi-solid in 81.4% yield(12 g) and was believed to be of the formula

wherein —C₃₄H_(56+a)— represents a branched alkylene group which mayinclude unsaturations and cyclic groups, wherein a is an integer of 0,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 and n is 1, including (but notlimited to) isomers of the formula

wherein n is 1.

EXAMPLE VII

The process of Example I was repeated except that the ethoxylatedhydroxyethyl methacrylate (CD570) was replaced withdi(ethyleneglycol)vinyl ether, available from Sigma-Aldrich FineChemicals, Milwaukee, Wis. The resulting product was obtained as a whitesemi-solid in 74.8% yield (4.96 g) and was believed to be of the formula

wherein —C₃₄H_(56+a)— represents a branched alkylene group which mayinclude unsaturations and cyclic groups, wherein a is an integer of 0,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 and n is 1, including (but notlimited to) isomers of the formula

wherein n is 1.

EXAMPLE VIII

A compound of the formula

wherein —C₃₄H_(56+a)— represents a branched alkylene group which mayinclude unsaturations and cyclic groups, wherein a is an integer of 0,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 and n is 1, including (but notlimited to) isomers of the formula

wherein n is 1 was prepared as follows. To a 3 neck, 250 mL round bottomflask equipped with a thermocouple, stir bar, stopper, Dean-Stark trap,reflux condenser, and argon inlet was added PRIPOL 1009 (C36 dimer acidmixture, including isomers of the formula

as well as other branched isomers which may include unsaturations andcyclic groups; 100 g, acid number 196 mgKOH/g, 95 wt %, obtained fromUniqema, New Castle, Del., (further information on C36 dimer acids ofthis type is disclosed in, for example, “Dimer Acids,” Kirk-OthmerEncyclopedia of Chemical Technology, Vol. 8, 4^(th) Ed. (1992), pp. 223to 237), the disclosure of which is incorporated herein by reference)and IRGAFOS 168 (tris(2,4-di-(tert)-butylphenyl)phosphate), 0.20 g, 0.2wt %, obtained from Ciba Specialty Chemicals, Basel, Switzerland). Thesystem was purged with Ar for 15 minutes with one of the necks open,after which time the stopper was replaced. The temperature was set to100° C. and the stirrer was set in motion. The stopper was quicklyreplaced with an addition funnel equipped with a septum and ethylenediamine (EDA, 5.25 g, 5.84 mL, 5 wt %, obtained from Sigma-AldrichChemical Company, Milwaukee, Wis.) was added to it via syringe. The EDAwas added to the reaction mixture slowly dropwise, ensuring that theinternal reaction temperature did not exceed 118° C. After the additionwas complete, the temperature was raised slowly stepwise to 155° C.,where it was kept until the water ceased collecting in the Dean-Starktrap (about 1.4 mL H₂O collected; reaction time was 2-3 h at 155° C.).The completion of the reaction was confirmed by ¹H NMR analysis inCDCl₃: the triplet at 62.34, corresponding to the protons alpha to thecarboxylic acid groups, and the triplet at 62.18, corresponding to theprotons alpha to the carbonyl groups of the amides, were approximatelyin a 1:1 ratio. At the end of the reaction, the temperature was loweredto 130° C. and the clear, amber oil was poured from the flask intoaluminum plates (recovered m=93 g). Acid number=101.1 mgKOH/g. ¹H NMR(CDCl₃, 300 MHz) 63.38 (4H, br. s), 2.53 (2H, br. s), 2.34 (4H, t, J=7.3Hz), 2.18 (4H, t, J=7.6 Hz), 1.88-0.65 (138H, m).

EXAMPLE IX

A compound of the formula

wherein —C₃₄H_(56+a)— represents a branched alkylene group which mayinclude unsaturations and cyclic groups, wherein a is an integer of 0,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 and n is 1, including (but notlimited to) isomers of the formula

wherein n is 1 was prepared as follows. To a 3 neck, 2 L flask equippedwith two dropping funnels, stir bar and argon inlet was added theoligoamide prepared as described in Example VIII (50 g, acid number101.1, n_(acid)=9.01×10⁻² mol), 4-dimethylaminopyridine (1.10 g,9.01×10⁻³ mol, obtained from Sigma-Aldrich Chemical Company, Milwaukee,Wis.) and methylene chloride (1 L) and the reaction mixture was stirreduntil homogenous. N,N′-Dicyclohexylcarbodiimide (99 mL, 1 M solution inCH₂Cl₂, 9.90×10⁻² mol, obtained from Sigma-Aldrich Chemical Company) wasadded slowly dropwise and the reaction mixture was allowed to stir for0.5 h before adding caprolactone acrylate (TONE M-100, 31.0 g, 9.01×10⁻²mol, obtained from Dow Chemical Company, Midland, Mich.). The reactionprogress was followed via ¹H NMR spectroscopy in CDCl₃: when the signalcorresponding to the methylene protons alpha to the hydroxyl group(˜δ3.6, t) were consumed, the reaction was complete. The reaction timewas between 2-3 h. The reaction mixture was filtered to removeN,N′-dicyclohexylurea (byproduct) and the filtrate solvent was removedin vacuo. The residue was redissolved in a minimum amount of CH₂Cl₂,refiltered, and concentrated in vacuo. The residue was triturated withacetone and filtered to reveal an off-white solid (m=45 g). ¹H NMR(CDCl₃, 300 MHz) 66.38 (2H, d, J=15.8 Hz), 6.20 (2H, dd, J=15.8, 10.5Hz), 5.89 (2H, d, J=10.5 Hz), 4.38-4.32 (8H, m), 4.09 (8H, t, J=6.6 Hz),3.38 (4H, s), 2.53 (2H, br. s), 2.38-2.27 (12H, m), 2.18 (4H, t, J=7.6Hz), 1.81-0.83 (162H, m).

EXAMPLE X

The process of Examples VIII and IX is repeated except that thecaprolactone acrylate is replaced with an equimolar amount ofethoxylated hydroxyethyl methacrylate CD570, available from SartomerCompany Inc. Exton, Pa.). It is believed that the product will be of theformula

wherein —C₃₄H_(56+a)— represents a branched alkylene group which mayinclude unsaturations and cyclic groups, wherein a is an integer of 0,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, including (but not limited to)isomers of the formula

wherein n is 1.

EXAMPLE XI

The process of Examples VIII and IX is repeated except that thecaprolactone acrylate is replaced with an equimolar amount ofpolypropylene glycol monomethacrylate, available as SR604 from SartomerCompany Inc., Exton, Pa. It is believed that the product will be of theformula

wherein —C₃₄H_(56+a)— represents a branched alkylene group which mayinclude unsaturations and cyclic groups, wherein a is an integer of 0,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 and n is 1, including (but notlimited to) isomers of the formula

wherein n=1.

EXAMPLE XII

The process of Examples VIII and IX is repeated except that thecaprolactone acrylate is replaced with an equimolar amount of2-hydroxyethyl acrylate, available from Sigma-Aldrich Fine Chemicals. Itis believed that the product will be of the formula

wherein —C₃₄H_(56+a)— represents a branched alkylene group which mayinclude unsaturated and cyclic groups, wherein a is an integer of 0, 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 and n is 1, including (but notlimited to) isomers of the formula

where n is 1.

EXAMPLE XIII

The process of Examples VIII and IX is repeated except that thecaprolactone acrylate is replaced with an equimolar amount of1,4-butanediol vinyl ether, available from Sigma-Aldrich Fine Chemicals,Milwaukee, Wis. It is believed that the product will be of the formula

wherein —C₃₄H_(56+a)— represents a branched alkylene group which mayinclude unsaturations and cyclic groups, wherein a is an integer of 0,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 and n is 1, including (but notlimited to) isomers of the formula

wherein n is 1.

EXAMPLE XIV

The process of Examples VIII and IX is repeated except that thecaprolactone acrylate is replaced with an equimolar amount ofdi(ethyleneglycol)vinyl ether, available from Sigma-Aldrich FineChemicals, Milwaukee, Wis. It is believed that the product will be ofthe formula

wherein —C₃₄H_(56+a)— represents a branched alkylene group which mayinclude unsaturations and cyclic groups, wherein a is an integer of 0,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 and n is 1, including (but notlimited to) isomers of the formula

wherein n is 1.

EXAMPLE XV

The process of Example I is repeated except that the ethoxylatedhydroxyethyl methacrylate (CD570) is replaced with polypropylene glycolmonomethacrylate, available as SR604 from Sartomer Company Inc., Exton,Pa. It is believed that the resulting product will be of the formula

wherein —C₃₄H_(56+a)— represents a branched alkylene group which mayinclude unsaturations and cyclic groups, wherein a is an integer of 0,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 and n is 1, including (but notlimited to) isomers of the formula

wherein n=1.

GPC Results

The molecular weight (weight average and number average) of some of thecompounds thus prepared were measured by elution in THF through fiveWaters Styragel columns: HR1, HR3, HR4, HR5, HR6. The column set wascalibrated against polystyrene and the molecular weights were expressedas polystyrene molecular weight equivalents. The solvent pumping systemwas a Waters Model 2695, and detection was provided by a Waters Model410 refractive index detector. The results are shown in the table below:M_(n) (×1000) M_(w) (×1000) P_(d) (M_(w)/M_(n)) Example I 2.7 4.7 1.74Example II 2.2 3.2 1.45 Example III 2.8 4.0 1.42 Example IX 2.4 3.6 1.50

INK EXAMPLE A

A phase change ink was prepared containing 6.32 percent by weight of acompound prepared as described in Example III, 2 percent by weight ofisopropyl-9H-thioxanthen-9-one (ITX, obtained from Ciba SpecialtyChemicals, Tarrytown, N.Y.), 3 percent by weight of alpha amino ketone(Irgacure 379, obtained from Ciba Specialty Chemicals), 3 percent byweight of1-[4-2-hydroxyethoxy-phenyl]-2-hydroxy-2-methyl-1-propane-1-one(photoinitiator; IRGACURE 2959, obtained from Ciba Specialty Chemicals),0.2 percent by weight of IRGASTAB UV10 (photoinitiator; obtained fromCiba Specialty Chemicals), 77.98 percent by weight of propoxylatedneopentyl glycol diacrylate (SR9003, obtained from Sartomer Co. Inc.,Exton, Pa.), and 7.5 percent by weight of blue SUN pigment dispersionUVD-B154 (obtained from Sun Chemical, Parsippany, N.J.). The gellantmaterial was first dissolved in the propoxylated neopentyl glycoldiacrylate, to which was added a mixture of photoinitiators consistingof isopropyl-9H-thioxanthen-9-one (ITX), alpha amino ketone (Irgacure379), 1-[4-2-hydroxyethoxy-phenyl]-2-hydroxy-2-methyl-1-propane-1-one(IRGACURE 2959), followed by IRGASTAB UV10, followed lastly by UVB-B154blue pigment dispersion. Rheological characteristics of this ink wereobtained by testing with a Rheometrics Fluid Spectrometer RFS3. Atemperature sweep from 90° C. to 30° C. at 1 Hz sweep rate was conductedwith measurements every five degrees. Complex viscosity of the ink at80° C. was 9.365 mPa s. Complex viscosity of the ink at 40° C. was6.08×10⁵ mPa s. G′ of the ink at 30° C. was 3816.2 Pa.

Other embodiments and modifications of the present invention may occurto those of ordinary skill in the art subsequent to a review of theinformation presented herein; these embodiments and modifications, aswell as equivalents thereof, are also included within the scope of thisinvention.

The recited order of processing elements or sequences, or the use ofnumbers, letters, or other designations therefor, is not intended tolimit a claimed process to any order except as specified in the claimitself.

1. A phase change ink comprising a colorant, an initiator, and a phasechange ink carrier, said carrier comprising at least one radicallycurable monomer compound and a compound of the formula

wherein R₁ and R₁′ each, independently of the other, is (i) an alkylgroup having at least one ethylenic unsaturation therein, includinglinear and branched, cyclic and acyclic, and substituted andunsubstituted alkyl groups, and wherein hetero atoms either may or maynot be present in the alkyl group, (ii) an arylalkyl group having atleast one ethylenic unsaturation therein, including substituted andunsubstituted arylalkyl groups, wherein the alkyl portion of thearylalkyl group can be linear or branched, cyclic or acyclic, andsubstituted or unsubstituted, and wherein hetero atoms either may or maynot be present in either the aryl or the alkyl portion of the arylalkylgroup, or (iii) an alkylaryl group having at least one ethylenicunsaturation therein, including substituted and unsubstituted alkylarylgroups, wherein the alkyl portion of the alkylaryl group can be linearor branched, cyclic or acyclic, and substituted or unsubstituted, andwherein hetero atoms either may or may not be present in either the arylor the alkyl portion of the alkylaryl group, R₂, R₂′, and R₃ each,independently of the others, are (i) alkylene groups, including linearand branched, saturated and unsaturated, cyclic and acyclic, andsubstituted and unsubstituted alkylene groups, and wherein hetero atomseither may or may not be present in the alkylene group, (ii) arylenegroups, including substituted and unsubstituted arylene groups, andwherein hetero atoms either may or may not be present in the arylenegroup, (iii) arylalkylene groups, including substituted andunsubstituted arylalkylene groups, wherein the alkyl portion of thearylalkylene group can be linear or branched, saturated or unsaturated,cyclic or acyclic, and substituted or unsubstituted, and wherein heteroatoms either may or may not be present in either the aryl or the alkylportion of the arylalkylene group, or (iv) alkylarylene groups,including substituted and unsubstituted alkylarylene groups, wherein thealkyl portion of the alkylarylene group can be linear or branched,saturated or unsaturated, cyclic or acyclic, and substituted orunsubstituted, and wherein hetero atoms either may or may not be presentin either the aryl or the alkyl portion of the alkylarylene group, and nis an integer representing the number of repeat amide units and is atleast
 1. 2. An ink according to claim 1 wherein R₁ and R₁′ are the sameas each other.
 3. An ink according to claim 1 wherein R₁ and R₁′ areboth alkyl groups having at least one ethylenic unsaturation therein,including linear and branched, cyclic and acyclic, and substituted andunsubstituted alkyl groups, and wherein hetero atoms either may or maynot be present in the alkyl group.
 4. An ink according to claim 3wherein the alkyl groups are unsubstituted alkyl groups.
 5. An inkaccording to claim 1 wherein R₁ and R₁′ are each of the formula

wherein m is an integer representing the number of repeating [O—(CH₂)₂]units.
 6. An ink according to claim 1 wherein R₂ and R₂′ are bothalkylene groups, including linear and branched, saturated andunsaturated, cyclic and acyclic, and substituted and unsubstitutedalkylene groups, and wherein hetero atoms either may or may not bepresent in the alkylene group.
 7. An ink according to claim 6 whereinthe alkylene groups are saturated unsubstituted alkylene groups.
 8. Anink according to claim 1 wherein R₂ and R₂′ are each groups of theformula —C₃₄H_(56+a)— and are branched alkylene groups which may includeunsaturations and cyclic groups, wherein a is an integer of 0, 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11, or
 12. 9. An ink according to claim 8 whereinR₂ and R₂′ include isomers of the formula


10. An ink according to claim 1 wherein R₃ is an alkylene group,including linear and branched, saturated and unsaturated, cyclic andacyclic, and substituted and unsubstituted alkylene groups, and whereinhetero atoms either may or may not be present in the alkylene group. 11.An ink according to claim 10 wherein the alkylene group is a saturatedunsubstituted alkylene group.
 12. An ink according to claim 1 wherein R₃is a —CH₂CH₂— group.
 13. An ink according to claim 1 wherein n is 1 or2.
 14. An ink according to claim 1 wherein the compound is of theformula

wherein —C₃₄H_(56+a)— represents a branched alkylene group which mayinclude unsaturations and cyclic groups, wherein a is an integer of 0,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 and wherein n is 1 or
 2. 15. Anink according to claim 1 wherein the compound is of the formula


16. An ink according to claim 1 wherein the compound is of the formula

or mixtures thereof, wherein —C₃₄H_(56+a)— represents a branchedalkylene group which may include unsaturations and cyclic groups,wherein a is an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12,n is 1 or 2, and m is an integer representing the number of repeating[O—(CH₂)₂] units.
 17. An ink according to claim 1 wherein the compoundis of the formula

or mixtures thereof, wherein n is 1 or 2 and m is an integerrepresenting the number of repeating [O—(CH₂)₂] units.
 18. An inkaccording to claim 1 wherein the compound of the formula

is present in the ink in an amount of at least about 5 percent by weightof the ink carrier.
 19. An ink according to claim 1 wherein the compoundof the formula

is present in the ink in an amount of no more than about 50 percent byweight of the ink carrier.
 20. An ink according to claim 1 wherein theradically curable monomer compound is propoxylated neopentyl diacrylate,isobornyl acrylate, isobornyl methacrylate, lauryl acrylate, laurylmethacrylate, isodecylacrylate, isodecylmethacrylate, caprolactoneacrylate, 2-phenoxyethyl acrylate, isooctylacrylate,isooctylmethacrylate, butyl acrylate, or mixtures thereof.
 21. An inkaccording to claim 1 wherein the carrier further contains amultifunctional acrylate or methacrylate compound.
 22. An ink accordingto claim 21 wherein the multifunctional acrylate or methacrylatecompound is pentaerythritol tetraacrylate, pentaerythritoltetramethacrylate, 1,2-ethylene glycol diacrylate, 1,2-ethylene glycoldimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanedioldimethacrylate, 1,12-dodecanol diacrylate, 1,12-dodecanoldimethacrylate, tris(2-hydroxy ethyl)isocyanurate triacrylate,hexanediol diacrylate, tripropylene glycol diacrylate, dipropyleneglycol diacrylate, amine modified polyether acrylate, trimethylolpropanetriacrylate, glycerol propoxylate triacrylate, dipentaerythritolpentaacrylate, dipentaerythritol hexaacrylate, ethoxylatedpentaerythritol tetraacrylate, or mixtures thereof.
 23. An ink accordingto claim 1 wherein the colorant is present in the ink in an amount of atleast about 0.1 percent by weight of the ink and wherein the color ispresent in the ink in an amount of no more than about 8 percent byweight of the ink.
 24. A process which comprises (I) incorporating intoan ink jet printing apparatus a phase change ink composition comprisinga colorant, an initiator, and a phase change ink carrier, said carriercomprising at least one radically curable monomer compound and acompound of the formula

wherein R₁ and R₁′ each, independently of the other, is (i) an alkylgroup having at least one ethylenic unsaturation therein, includinglinear and branched, cyclic and acyclic, and substituted andunsubstituted alkyl groups, and wherein hetero atoms either may or maynot be present in the alkyl group, (ii) an arylalkyl group having atleast one ethylenic unsaturation therein, including substituted andunsubstituted arylalkyl groups, wherein the alkyl portion of thearylalkyl group can be linear or branched, cyclic or acyclic, andsubstituted or unsubstituted, and wherein hetero atoms either may or maynot be present in either the aryl or the alkyl portion of the arylalkylgroup, or (iii) an alkylaryl group having at least one ethylenicunsaturation therein, including substituted and unsubstituted alkylarylgroups, wherein the alkyl portion of the alkylaryl group can be linearor branched, cyclic or acyclic, and substituted or unsubstituted, andwherein hetero atoms either may or may not be present in either the arylor the alkyl portion of the alkylaryl group, R₂, R₂′, and R₃ each,independently of the others, are (i) alkylene groups, including linearand branched, saturated and unsaturated, cyclic and acyclic, andsubstituted and unsubstituted alkylene groups, and wherein hetero atomseither may or may not be present in the alkylene group, (ii) arylenegroups, including substituted and unsubstituted arylene groups, andwherein hetero atoms either may or may not be present in the arylenegroup, (iii) arylalkylene groups, including substituted andunsubstituted arylalkylene groups, wherein the alkyl portion of thearylalkylene group can be linear or branched, saturated or unsaturated,cyclic or acyclic, and substituted or unsubstituted, and wherein heteroatoms either may or may not be present in either the aryl or the alkylportion of the arylalkylene group, or (iv) alkylarylene groups,including substituted and unsubstituted alkylarylene groups, wherein thealkyl portion of the alkylarylene group can be linear or branched,saturated or unsaturated, cyclic or acyclic, and substituted orunsubstituted, and wherein hetero atoms either may or may not be presentin either the aryl or the alkyl portion of the alkylarylene group, and nis an integer representing the number of repeat amide units and is atleast 1, said ink being curable upon exposure to ultraviolet radiation;(II) melting the ink; (III) causing droplets of the melted ink to beejected in an imagewise pattern onto a substrate; and (IV) exposing theimagewise pattern to ultraviolet radiation.
 25. A process according toclaim 24 wherein the substrate is a final recording sheet and dropletsof the melted ink are ejected in an imagewise pattern directly onto thefinal recording sheet and the imagewise pattern on the final recordingsheet is exposed to ultraviolet radiation.
 26. A process according toclaim 24 wherein the substrate is an intermediate transfer member anddroplets of the melted ink are ejected in an imagewise pattern onto theintermediate transfer member followed by transfer of the imagewisepattern from the intermediate transfer member to a final recordingsheet, and wherein the imagewise pattern on the final recording sheet isexposed to ultraviolet radiation.
 27. A process according to claim 26wherein the intermediate transfer member is heated to a temperatureabove that of the final recording sheet and below that of the melted inkin the printing apparatus.